Skin-contact product having moisture and microclimate control

ABSTRACT

Skin-contact products with a transpiration function such as medical devices or medicinal products, of which face masks, aspirators, ventilators, breast pumps or wound dressings are examples are described especially a skin-contact product with a transpiration function with an improved microclimate at a patient interface material-skin contact area. In an embodiment a material system is described that comprises a hydrophobic silicone base material and a hydrophilic silicone material that is combined with the hydrophobic base material.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Division of U.S. patent application Ser. No.15/447,198, filed Mar. 2, 2017, that issued as U.S. Pat. No. 6,043,328on Mar. 28, 2000, which is a Continuation of U.S. patent applicationSer. No. 14/127,538, filed Dec. 19, 2013, that was abandoned on Sep. 16,2019, which claims priority under 35 U.S.C. § 119(e) from provisionalU.S. patent application No. 61/586,876 filed Jan. 16, 2012, andprovisional U.S. patent application No. 61/502,961 filed Jun. 30, 2011,the contents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to skin-contact products with moisture andmicroclimate control such as medical devices or medicinal products,especially user or patient interface devices of which face masks,respiratory masks, aspirators, ventilators, breast pumps or wounddressings are examples and, more particularly, to a skin-contact productwith a transpiration function with an improved microclimate at a patientinterface-skin contact area.

2. Description of the Related Art

There are many medical applications which require gas exchange, e.g.pressure to be applied to the skin of a human or other animal over along period of time where a microclimate is created that may beuncomfortable for the wearer. Examples are patient interface devices,respiratory masks, aspirators, ventilators, breast pumps, and wounddressings.

An exemplary medical application relates to a patient interface deviceused for ventilation for positive air pressure or oxygen delivery.Positive air pressure (PAP) is a method of respiratory ventilation usedprimarily for the treatment of sleep disorders such as obstructive sleepapnea (OSA). Sleep apnea is a sleep disorder characterized by abnormalpauses in breathing or instances of abnormally low breathing, duringsleep. Each pause in breathing, called an apnea, can last from a fewseconds to minutes, and may occur 5 to 30 times or more an hour.Similarly, each abnormally low breathing event is called a hypopnea.Sleep apnea is diagnosed with an overnight sleep test called apolysomnogram, or “sleep study”. There are three forms of sleep apnea:central (CSA), obstructive (OSA), and complex or mixed sleep apnea (i.e.a combination of central and obstructive). In CSA, breathing isinterrupted by a lack of respiratory effort; in OSA, breathing isinterrupted by a physical block to airflow despite respiratory effort,and snoring is common.

A patient interface mask required to deliver PAP must have an effectiveseal and needs to be held on securely. A patient interface device is,for example, disclosed in the International patent applicationsWO2007/012140 and WO2008/070929. Many people find wearing the patientinterface device uncomfortable to such an extent that use of the deviceis discontinued. Wearing a patient interface device, patients arereporting skin irritation, red marks and skin breakdown. The recoverytime varies from minutes to hours but in extreme cases, longer-lastingskin damage and pressure sores can occur. These skin problems result inlow patient compliance with patient interface devices and CPAP therapy.

The root causes for formation of red marks in the face of a personwearing a patient interface device are manifold and not yet fullyunderstood. Common factors reported in tissue breakdown are excessivemechanical skin load by pressure, shear and friction.

In general, mechanical skin loading by pressure, shear and friction canlead to multiple effects:

-   -   Ischemia: the occlusion of capillary blood vessels.    -   Reperfusion injury: after unloading, accumulated free radicals        are released and cause inflammation and cell damage.    -   Lymphatic function impairment: occlusion and damage of the lymph        vessels prevents the removal of metabolic waste, leading to        tissue necrosis.    -   Mechanical deformation of tissue cells: cell membranes rupture,        volume changes of cells leads to initial damage, and        cytoskeletal reorganization occurs.    -   Moisture accumulation in the skin due to coverage of the skin        decreases the skin strength to damage.

The materials of choice in current patient interface devices, such asPAP patient interface masks, are silicone rubbers because of thebiocompatibility they provide. Silicone materials, a group of materialsbased on various types of polysiloxanes, are typically highly stableagainst chemical modification and aging and, therefore, guarantee for along shelf life and time of use.

Silicone rubbers can be made via three different major industrialmethods. The platinum salt catalyst induced method (applicable to vinyland SiH containing silicone prepolymers) is the preferred method as itgives medical grade materials. The two other methods, i.e. peroxidecrosslinking of vinyl-containing silicone prepolymers or tin saltcatalyst induced crosslinking of silanol containing siliconeprepolymers, are less preferred for skin contacting areas but can beoption for other, non skin contacting parts of the patient interface.These materials are intrinsically hydrophobic and have very low waterpermeability, and, thus, do not provide a suitable environment forgrowth of bacteria and harmful bio-films. As a result of theseproperties, silicone materials can function as a tight seal in thoseareas of a person's face, where they are in contact with the skin. Theseare typically all areas in which a patient interface device contacts theface. While a tight seal is desired, the hydrophobic materials are notvery suitable to allow transport of moisture and sweat, which attributesto the red mark formation and discomfort.

As another example, a wound dressing is known with which a screen isplaced over substantially the whole surface of the wound. The size andconfiguration of the screen can be adjusted to fit the individual wound.It can be formed from a variety of porous semi-rigid materials. Thematerial must be sufficiently porous to allow oxygen to reach the wound,and sufficiently rigid to prevent wound overgrowth, for example the useof an open-cell polymer foam is known. Some designs of wound dressingrequire direct connection of the screen to a vacuum pump through aflexible hose inserted into the foam. Such foam can vary in thicknessand rigidity, although it is preferred that a spongy material be usedfor the patient's comfort if the patient must lie upon the device duringits operation.

The molecular design and synthesis of hydrophilic silicone materials isa relatively unexplored area. Still, some hydrophilic silicone materialshave been disclosed in the known prior art. For example, patentapplication publication No. US2002/0160139 discloses a surface modifiedpolymer including a surface that is covalently bonded to a surfacemodifying compound. Formation of the covalent bond between the polymerand the surface modifying compound is achieved by a reaction between anintrinsic functional group that is present in the polymer and thefunctional group of the surface modifying compound. By using a polymerhaving an intrinsic functional group, a separate surface activation stepis avoided. Thus, the material has a hydrophilic surface while the bulkof the material remains hydrophobic. Accordingly, this material does notallow for the uptake of moisture or diffusion of moisture through thematerial and moisture can, thus, not be removed effectively from acontact area.

Another known prior art example in the field of hydrophilic siliconematerials is International patent application WO2010/905105, whichdiscloses a novel microfluidic system having a substrate based on rubbermaterial having polar side groups that are linked to the rubber polymerbackbone via a spacer. This arrangement provides for a transport ofwater-based fluids such as blood or saliva by capillary forces. Theprovided material has a hydrophilic surface as well as hydrophilic bulkproperties allowing for a beneficial use in microfluidic devicesintended for use with aqueous solutions. The rubber material includespolar side groups that are linked with the polymer chain of the rubbermaterial via a carbon chain (linker) comprising at least 6 atoms. Therubber material is made by a process including the step of radicaladdition of a suitable rubber precursor monomer with anionic precursormaterial. By doing so, the rubber material may be produced relativelyeasy. The step of radical addition may be performed, for example, byradical dimerization of alkene moieties or by any other known bondingtechnique in the field. It may be performed by a radical initiator, suchas peroxides or tin organyls, or by UV-light. More specifically, thepolar side groups may be ionic side groups such as —SO3-. For instancethe material may be a silicone rubber modified with 15-20 w % sodiumalkene C₁₄₋₁₆ sulfonate. The silicone rubber may have a chain lengthfrom 1000 to 10000 Si—O units, and the modified silicone rubber may bemade by radical addition of ω-alkenylsulfonic acids to siloxane unitspresent in the polysiloxane chain.

More generally, many commercial polymers are not skin friendly as theydo not absorb water or sweat from the skin.

Introduction of an alpha-olefin sulfonate surfactant into these polymersmay provide a copolymer with an increased hydrophilic character whichcan be used to increase its biocompatibility and its capacity to holdwater. For the manufacture of skin-contact products, this is especiallyrelevant to biocompatible polymers such as, but not limited to,silicones, polybutadiene, polybutadiene-containing polymers,polybutadiene-polyethylene oxides copolymers, poly(meth)acrylates, andisobutylene-ethylene glycol copolymers.

However alpha-olefin sulfonate surfactants, although having a vinylfunctional group, do not easily mix with the monomer of commercialpolymers like polyethylene (PE), polypropylene (PP), polybutadiene,polyisoprene, polystyrene (PS), polyacetonitrile (PAN), silicones,poly(meth)acrylates, polyacrylonitrile, acrylonitrile-butadiene-styrenecopolymers (ABS) and styrene-acrylonitrile copolymers (SAN). Thisincompatibility can be due to differences in boiling points, makingthese non volatile surfactants nearly impossible to use in gas phasepolymerizations. Even under liquid phase polymerization conditions, itis difficult to mix a hydrophilic surfactant containing a sulfonic acidsalt with a hydrophobic monomer or pre-polymer. Only in a special caselike the suspension polymerization of vinyl chloride in water, can thehydrophilic surfactant be dissolved in a part of the reaction mixture(water) and thus incorporated into the main polymer. However polyvinylchloride is not regarded as a skin-compatible polymer.

Despite this effort, there is still a need for an improved microclimateat a device-skin contact area, which is well suited to reduce moistureaccumulation in the skin, which decreases skin strength, and ultimatelythe formation of red marks. Further, there is also a need for a widerrange of polymer materials, in particular silicone rubber materials,with hydrophilic bulk properties for use as an aid to moisture control,in particular for manufacturing devices with moisture control propertieslike face masks, such as patient interface masks for positive airpressure (PAP) therapy of obstructive sleep apnea (OSA), and wounddressings.

SUMMARY OF THE INVENTION

It is a principal object of embodiments of the present invention toprovide a skin-contact product with moisture and microclimate controlsuch as medical devices or medicinal products, health care or safety oremergency products, of which user or patient interface devices,respiratory masks, aspirators, ventilators, breast pumps or wounddressings are examples. The moisture and microclimate control can beprovided by materials in contact with the skin having a transpirationfunction.

An advantage of a skin-contact product with moisture and microclimatecontrol according to embodiments of the present invention is theprovision of an improved microclimate at a material skin interface, e.g.when used in a user interface device. This can be achieved by using amaterial system for the product, e.g. for a user or patient interfacedevice that reduces moisture accumulation in and on the skin. Thespecial feature of this skin contact product is that due to themicroclimate control, moisture increase at the interface of the skin andskin contact product as well as stratum corneum hyper-hydration can beprevented. In this way the decrease of the tensile strength of the skindue to moisture uptake can be prevented.

The skin contact product thus contributes to tissue tolerance to shearstress and friction and thus to less damage of the skin for exampleduring wearing a user or patient interface device. The skin contractproduct thus improves comfort of a user or patient interface device andsupports the reduction of red mark formation and skin irritation forexample if a patient interface mask is applied to the skin.

The object of the invention can be achieved by making use of materialsystems that include composites of different materials or materialsystems with well defined material stacks, with which moisture uptake aswell as moisture penetration may be realized in the material whileproviding improved product stability on the skin.

In one aspect the present invention provides skin contact product suchas a user interface adapted for use in a system for communicating a flowof gas with a user, the user interface comprising a user contactingassembly having a first portion comprising (1) a support material, and(2) a contact structure comprising moisture uptake means that isnon-releasably combined with and supported by the support material,wherein the contact structure is adapted so that the moisture uptakemeans at least partially contacts a skin surface of a user responsive tothe user interface being worn by such a user wherein the supportmaterial provides mechanical and dynamical stability for the moistureuptake means, or the first portion of the user contact assembly, andwherein the moisture uptake means allows for uptake or diffusion ofmoisture from a skin surface of a user over which the user contactingassembly is disposed.

In accordance with embodiments of the present invention user contactingassembly can reduce moisture accumulation, irritation and red markformation when in contact with the skin of a person and in this wayimproves comfort. In any of the embodiments of the present invention,moisture uptake means or any other part of the device may includeanti-bacteria, and anti fungi agents such as silver compounds, or ananti-viral agent such as a microbiocide, all or any of these being in orcoated on any material in contact with the skin of the user.

The moisture uptake means can be provided by a variety of materials ormaterial systems such as a hydrophilic material that absorbs water, ahydrophilic material formed with capillaries which take up water, ahydrophobic material formed with capillaries which take up water, etc.The take up of water into the material can result in softening orweakening of the material and the support material has the purpose ofsupporting such weakened material. Hence the moisture uptake means cancomprise a hydrophilic material or a hydrophobic material depending onhow it is structured and used. In embodiments the hydrophilic materialcan be a textile integrated in the contact structure. Preferably such amaterial is adapted so that said textile at said skin surface of a useris crease-free and/or leak-free. The hydrophilic material can be arubber material that takes up at least 5% by weight of water, preferablymore that 10% by weight of water and particularly preferably more than40% up to 120% by weight of water, or up to 200% or up to 250% or up to500% by weight of water after immersion in demineralized water at roomtemperature for a sufficient time such as 5 days or more to reachsaturation. It is expected that with increasing water absorption themechanical properties may be reduced such that a support material is notonly necessary but must be designed in a form that will stabilise thehydrophilic material.

Hence, the interface may comprise a support portion, the first portionbeing operatively coupled to the support portion. This support portionmay be a shell, such as a transparent shell or dome. This may cover themouth, the nose, the mouth and nose of the patient. The support portioncan be form stable. The support portion can be adapted to receive a gasconnection for gas exchange which can be either pressurised gas such asair or a vacuum or both. Hence, a gas transfer port or a gas exchangeport may be located in the support portion for the purposes ofcommunicating a gas flow.

Communicating a gas flow means that a gas pressure is developed that canbe either a positive or negative pressure. To avoid loss or leak of gas,a seal can be provided for forming a gas exchange sealing contact withskin of a user. This seal may be integrated into user contactingassembly or may be separate.

In embodiments the support material comprises a hydrophobic material ora hydrophilic material, preferably a rubber material. The rubbermaterial can be any of silicone, latex, and polybutadiene or othermaterials as disclosed below.

In accordance with a further embodiment of the present invention, andfollowing similar guiding principles as for the user interface devicehereinabove, there is also provided a wound dressing, e.g. a wounddressing with the application of vacuum, comprising a hydrophilicrubbery or elastomeric polymer material taking up at least 5% by weightof water, and up to 500% by weight of water after immersion indemineralized water at room temperature for a sufficient time to reachsaturation.

In further embodiments of the present invention hydrophilic polymermaterials are provided, e.g. hydrophilic rubber or elastomericmaterials, other than a hydrophilic silicone rubber material. This maybe achieved for example by providing a hydrophilic polyurethane.Hydrophilic polyurethanes can be made by coupling a diisocyanate monomeror pre-polymer with hydrophilic monomers or pre-polymers. Examples ofsuch hydrophilic monomers or pre-polymers include, but are not limitedto, glycerol, ethylene glycol derivatives, polyethylene glycol and otherhydroxyl function-containing polyol compounds. The hydrophilicproperties can be even further increased by coupling a hydrophilicpolyurethane with another hydrophilic polymer which does not necessarilycontain a hydroxyl group. The hydrophilic material can be any of:hydrophilic silicone, polyvinylpyrrolidones (usually with a numberaverage molecular weight from 20,000 to 400,000), poly(hydroxyethylmethacrylates), polyethylene glycols (usually with a number averagemolecular weight from 200 to 10,000), polyvinyl alcohols (usually with anumber average molecular weight from 10,000 to 150,000),polyacrylamides, alkali metal poly(meth)acrylates (such as, but notlimited to, sodium polyacrylate, potassium polyacrylate, sodiumpolymethacrylate, potassium polymethacrylate), and mixtures thereof orother materials as disclosed below.

In any of the embodiments of the present invention the hydrophilicmaterial moisture uptaking means, or any other part of the device, mayinclude one or more anti-bacterial agents, and/or one or more antifungal agents such as silver compounds, or one or more anti-viral agentssuch as a microbiocide, all or any of these being for instance presentin, or coated onto, any material in contact with the skin of the user.

In one embodiment of the present invention, said hydrophilic material isa hydrophilic silicone material and the hydrophobic material is ahydrophobic silicone material.

In another embodiment of the present invention said support material isa hydrophobic material that forms a base layer;

-   -   wherein said hydrophilic material is a hydrophilic silicone that        forms a first layer disposed over the base layer; and    -   wherein said first layer is adapted to be disposed against the        skin of a user responsive to the user interface being worn by        such a user.

In yet another embodiment of the present invention, said hydrophilicmaterial is mixed into said support material, said support materialbeing a hydrophobic material to form a composite mixture.

In a further embodiment of the present invention, a layer of hydrophobicmaterial is formed at an outside of said composite mixture;

-   -   wherein said layer is perforated forming apertures; and    -   wherein said apertures are for contacting said hydrophilic        material with the skin of a person.

In still another embodiment of the present invention, said supportmaterial is a hydrophobic material that includes a plurality of holespositioned at an interface of said hydrophobic material for contactingthe skin of a person;

-   -   wherein said holes are filled with said hydrophilic material;        and    -   wherein said hydrophilic material is for contact with the skin        of a person.

The user interface described in the present invention can be made in avariety of forms and may comprise a forehead pad and/or a nose/mouthcushion. Generally there will be means for securing the interface inplace, e.g. tapes, straps, bands etc which can be adjustable.

In various embodiments the support portion can be in the form of a shellhaving a rim, and wherein the user contacting assembly is attached tothe rim in a sealed manner.

Preferably the support material is stiffer than said hydrophilicmaterial when there has been uptake of moisture in said hydrophilicmaterial.

The user interface can be for use in a variety of systems such as systemfor communicating a flow of gas with an airway of a user.

In particular embodiments of the present invention, the user interfacedevice or the wound dressing make use of a hydrophilic rubber materialinstead of, or in combination with, the typical hydrophobic rubbermaterial, e.g. hydrophilic silicone material instead of or incombination with the typical hydrophobic silicone material. Thehydrophilic rubber material preferably takes up more than 5% by weightof water, preferably more than 10% by weight of water, particularlypreferably more than 20% and preferably more than 40% by weight up to120% by weight of water, or up to 200% by weight of water, up to 250% byweight of water, or up to 500% by weight of water after immersion indemineralized water at room temperature for a sufficient amount of time,such as 5 days or more, to reach saturation. In accordance withembodiments of the present invention user contacting assembly can reducemoisture accumulation, irritation and red mark formation when in contactwith the skin of a person and in this way improves comfort. In any ofthe embodiments of the present invention, moisture uptake means or anyother part of the device may include one or more anti-bacterial agents,and/or one or more anti fungal agents such as silver compounds, or oneor more anti-viral agents such as a microbiocide, all or any of thesebeing either present in or coated onto any material in contact with theskin of the user.

Accordingly, in one embodiment in accordance with the present invention,a combination of hydrophobic and hydrophilic materials such as, but notlimited to, a combination of hydrophobic and hydrophilic siliconematerials, near the product-skin interface is utilized. The combinationcan be used with a shell or enclosure, such as an airtight enclosurethat is part of a user or patient interface device or mask or similar.The enclosure can be made of rigid material or can be a semi-rigidmaterial having some flexibility provided it forms a form-stableenclosure. Such an enclosure can have a rim that forms a seal with theskin, e.g. a seal such as required for aspiration, ventilation etc. of aperson, or for the application of vacuum in a wound dressing. Hence theseal generally only needs to be suitable for positive or negativepressures (pressures up to 70 KPa and more). For example, a flap canextend around a rim or perimeter of the patient interface device and canbe made of a relatively flexible material to provide a leak resistantseal over the patient contacting area. However, according toembodiments, of the present invention at least part of the hydrophilicmaterial e.g. hydrophilic silicone material may be arranged such that,in use, it is in contact with the skin of a person. The hydrophobicmaterial such as hydrophobic silicone material can be adapted to ensuremechanical stiffness of the product having a user interface, such as apatient interface device or face mask. The hydrophilic material such ashydrophilic silicone material is adapted to allow transport of moistureand sweat to improve comfort, prevent moisture accumulation at the skinand stratum corneum hyper-hydration and prevent decrease of the tensilestrength of the skin. The material thus supports reduction of red markformation, skin irritation, skin damage if applied to the skin as e.g.patient interface device.

In one embodiment in accordance with the present invention, a layer of ahydrophilic material such as hydrophilic silicone material is placed ontop of a hydrophobic material such as hydrophobic silicone material suchthat it comes in contact with the skin of a person using theskin-contact product having a user interface. The contact can besuitable for forming a seal as mentioned above. In another embodiment inaccordance with the invention, the hydrophobic material such ashydrophobic silicone material includes openings in a surface that is incontact with the skin of a person during the use of the skin-contactproduct having a user interface, the openings being filled withhydrophilic material such as hydrophilic silicone material. The contactcan be suitable for forming a seal as mentioned above. In yet anotherembodiment in accordance with the invention, hydrophobic and hydrophilicmaterials such as hydrophobic and hydrophilic silicone materials aremixed resulting in some of the hydrophobic material and some of thehydrophilic material ending up at the skin-product cushion interface.The contact can be suitable for forming a seal as mentioned above. Ascan be seen, in each of these embodiments in accordance with theinvention, at least part of the hydrophilic material such as hydrophilicsilicone material is in contact with the skin of a person during the useof the skin-contact product having a user interface, such as a facemask. In each case, the skin contact can be suitable for forming a seal.

A water-absorbing rubbery or elastomeric polymer material useful as acomponent of a user interface device or a wound dressing according tothe present invention may be present under various forms. For instanceit may be in the form of a sheet, or a fiber, or a coating adapted foradhesion to a substrate, or a foam, e.g. a foam with a foam density from60 to 300 kg/m³.

It is a further and independent object of further embodiments of thepresent invention to provide novel compositions for the preparation ofhydrophilic silicone materials allowing for improved mixing andsynthesis processes resulting in improved hydrophilic bulk properties ofthe obtained hydrophilic silicone material. Such materials can besuitable for use in a skin-contact product with moisture andmicroclimate control such as a medical device or a medicinal product, ofwhich face masks, aspirators, ventilators, breast pumps or wounddressings are examples.

Such a hydrophilic material may allow for an effective removal ofmoisture from any user interface where it is used, for example from theskin-mask interface areas or from other devices such as wound dressings,by either uptake of the moisture in the hydrophilic silicone material orby diffusion of the moisture through the hydrophilic silicone away fromthe contact area. As a result, an improved microclimate at theskin-product interface areas is created, which may be well suited toimprove comfort, reduce skin irritation, reduce skin damage by lessmoisture accumulation and ultimately reduce the formation of red marks.

In a further and independent object of further embodiments of thepresent invention, the hydrophilic materials is another material than ahydrophilic silicone material, for example hydrophilic polyurethanes.Hydrophilic polyurethanes are made by coupling the diisocyanate monomeror pre-polymer with hydrophilic monomers or pre-polymers. Examples ofhydrophilic monomers or pre-polymers are glycerol, ethylene glycolderivatives, polyethylene glycol and other hydroxyl function containingpoly-ol compounds. The hydrophilic properties can be even furtherincreased by coupling this small chain hydrophilic polyurethane withother hydrophilic polymers which do not necessarily contains a hydroxylgroup. Examples of these more general hydrophilic polymers are:polyvinylpyrrolidones (usually with a number average molecular weightfrom 20,000 to 400,000), poly(hydroxyethyl methacrylates), polyethyleneglycols (usually with a number average molecular weight from 200 to10,000), polyvinyl alcohols (usually with a number average molecularweight from 10,000 to 150,000), polyacrylamides, alkali metalpoly(meth)acrylates (such as, but not limited to, sodium polyacrylate,potassium polyacrylate, sodium polymethacrylate, potassiumpolymethacrylate), and mixtures thereof. In accordance with embodimentsof the present invention user contacting assembly can reduce moistureaccumulation, irritation and red mark formation when in contact with theskin of a person and in this way improves comfort. In any of theembodiments of the present invention, hydrophilic materials may includeanti-bacteria, and anti fungi agents such as silver compounds, or ananti-viral agent such as a microbiocide, all or any of these being in orcoated on any material in contact with the skin of the user.

In a further and independent object of further embodiments of thepresent invention, the hydrophilic materials is yet another materialsuch as a textile based material, in which the fiber content isinherently moisture absorbing such as cellulose fibers (cotton, viscose)or silk and wool. Alternatively moisture absorption can be achieved dueto the textile structure such as woven, knitted, non-woven, or otherengineered fabrics such as spacer fabric.

In this embodiment the patient interface is either made fully out of thetextile based material to take moisture up and reduce red marks or itcan be a hybrid material with for example based on a rubber such as asilicone rubber combined with one or more layers of textile. To be ableto achieve the object of the invention, the present invention provides ahydrophilic rubber material that takes up more than 5% by weight ofwater, preferably more that 10% by weight of water and particularlypreferably more than 20% by weight and preferably more than 40% byweight or even up to 120% by weight of water, or up to 200% by weight ofwater, up 250% by weight of water, or 500% by weight of water afterimmersion in demineralized water at room temperature for a sufficientamount of time at room temperature, such as 5 days or more, to reachsaturation.

It is thus a further and independent object of further embodiments ofthe present invention to provide hydrophilic polymer materials, e.g.hydrophilic rubber or elastomeric materials, other than a hydrophilicsilicone rubber material. This may be achieved for example by providinga hydrophilic polyurethane. Hydrophilic polyurethanes can be made bycoupling a diisocyanate monomer or pre-polymer with hydrophilic monomersor pre-polymers. Examples of such hydrophilic monomers or pre-polymersinclude, but are not limited to, glycerol, ethylene glycol derivatives,polyethylene glycol and other hydroxyl function-containing polyolcompounds. The hydrophilic properties can be even further increased bycoupling a hydrophilic polyurethane with another hydrophilic polymerwhich does not necessarily contain a hydroxyl group. Examples of suchhydrophilic polymers include, but are not limited to:polyvinylpyrrolidones (usually with a number average molecular weightfrom 20,000 to 400,000), poly(hydroxyethyl methacrylates), polyethyleneglycols (usually with a number average molecular weight from 200 to10,000), polyvinyl alcohols (usually with a number average molecularweight from 10,000 to 150,000), polyacrylamides, alkali metalpoly(meth)acrylates (such as, but not limited to, sodium polyacrylate,potassium polyacrylate, sodium polymethacrylate, potassiumpolymethacrylate), and mixtures thereof.

Such a hydrophilic rubber material may be obtained by a processcomprising the steps of (a) providing a silicone precursor and ahydrophilic molecule or polymer, and (b) polymerizing said siliconeprecursor in the presence of said hydrophilic molecule or polymer and inthe optional presence of a solvent.

In this process the silicone precursor may or may not react with thehydrophilic polymer.

With respect to hydrophilic silicone rubber materials that do notcontact the skin or a mucosa, there is no limitation upon themanufacturing method by which they may be obtained, that is any of thethree crosslinking methods briefly mentioned above and further detailedhereinafter may be suitable, depending upon the medical or non-medicalapplication for which the hydrophilic silicone rubber material isintended, and depending the form (e.g. sheet, coating, fiber or foam) inwhich the water-absorbing silicone rubber material is desired.

The peroxide cross-linking method can give non medical grade hydrophilicsilicone rubbers by adding vinyl containing hydrophilic molecules, forexample an ethylenically unsaturated (olefinic) soap such as analpha-olefinic sulfonic acid sodium salt, to the silicone mixture. Otherreactive groups suitable for this reaction are allyl, acrylic ormethacrylic groups. The ethylenically unsaturated (olefinic) soap candirectly be added to the mixture and will thus be incorporated into thesilicone matrix by the radical cross-linking reaction, e.g. see scheme 1showing a simplified non-limiting overview of the peroxide cross-linkingof a vinyl-containing silicone prepolymer with vinyl containinghydrophilic molecules. In this scheme, R₁ and R₃ each designate residuegroups of the peroxide used to initiate cross-linking. R₂ is a hydrogenatom, an alkyl group or a trimethylsilyl group.

Suitable peroxides (R₁OOR₃) for this crosslinking reaction include, butare not limited to, for instance dicumyl peroxide,bis(2,4-dichlorobenzoyl) peroxide or2,5-bis-(tert.-butylperoxo)-2,5-dimethylhexane. As this cross-linkingpolymerization is based on radicals several hydrophilic or siliconecontaining molecules may be incorporated into the silicone matrix.

Non medical grade hydrophilic silicone rubbers can also be made by a tincatalyzed condensation polymerization but here the hydrophilic moleculesneed to contain a hydrolysable silane group. Suitable hydrolysablesilanes preferably contain one or more alkoxy or acetoxy groups whichare able to react in the silanol condensation reaction. As an example, asuitable molecule is 3-(trihydroxysilyl)-1-propanesulfonic acid (CAS70942-24-4) for instance commercially available from Gelest Inc.(Morrisville, Pa., USA), but molecules with other hydrophilic groupssuch as trialkoxysilane terminated polyglycols are also possible. Scheme2 below shows a simplified overview of the tin catalyzed cross linkingof silanol containing silicone prepolymers with hydrophilic moleculeswith an alkoxy- or acetoxysilane group. In this scheme, R₁ is H or ahydrolysable group like an alkoxy or an acetoxy group.

The third method is the preferred method to make medical grade siliconerubbers but can also be used for non medical applications. The presentinvention more specifically relates to hydrophilic silicone-based rubbermaterials having such high water uptake capacity at room temperaturethat they can be used for manufacturing skin-contact products, inparticular skin-contact products with a transpiration function. In otherembodiments, the water-absorbing (hydrophilic) silicone-based rubbermaterials of the present invention are suitable for contact with themucosa of a human.

The present invention also relates to polymerizable compositionscomprising both hydrophobic and hydrophilic monomers that can bepolymerized under liquid phase polymerization conditions, and topolymers and copolymers that can be obtained from such compositions. Thepresent invention more specifically relates to biocompatible polymersand copolymers comprising both hydrophobic and hydrophilic monomerunits. The hydrophilic monomer units can be incorporated in the mainchain or as a side group of the silicone polymer matrix. Incorporationinto the main chain is possible when the hydrophilic molecules containtwo or more active groups which can react in the cross-linking reaction.Possible molecules are sulfonic acid salt with two or more vinylicgroups or hydrophilic polymers with two or more side or terminal groupscontaining a double bond like an allyl group. A schematic overview ofthis reaction is given in scheme 3 showing the incorporation ofhydrophilic molecules into the silicone rubber matrix main chain,wherein the hydrophilic molecule has two reactive groups that canparticipate in the platinum catalyzed crosslinking reaction, and whereina suitable reactive group is an allyl group. Incorporation as a sidegroup is possible when the hydrophilic molecule contains only onereactive group that can react in the cross-linking reaction.

In one embodiment of the present invention, a hydrophilic silicone-basedrubber material comprises:

dialkylsiloxane (preferably dimethylsiloxane) and/or arylsiloxane(preferably methylphenyl siloxane or diphenylsiloxane) repeating units,and

at least one modified dialkylsiloxane or modified arylsiloxane repeatingunit wherein one alkyl or aryl group of said repeating unit is replacedwith a hydrophilic side group,

and is such that the total number of repeating units (a) and repeatingunits (b) is at least 5 and less than 1,000. The repeating units (a)form part of what is hereinafter called a “silicone precursor”. Therepeating units (a) may be of a single type (e.g. preferablydimethylsiloxane), or mixed types (e.g. dimethylsiloxane anddiphenylsiloxane) in any proportions. In the latter case, they may bearranged randomly in the polymer chain, or they may be arranged in theform of block copolymers, for instancepolydiphenylsiloxane-polydimethylsiloxane-polydiphenyl-siloxanetri-block copolymers.

In a broader aspect, it is a principal object of other embodiments ofthe present invention to provide a rubber or elastomeric material takingup more than 5% by weight of water and up to 120% by weight of water, orup to 200% by weight of water, up 250% by weight of water, or 500% byweight of water after immersion in demineralized water at roomtemperature for a sufficient amount of time, such as 5 days or more, toreach saturation, comprising:

-   -   (a) repeating units from one or more hydrophobic organic        monomers, and    -   (b) repeating units from one or more monomers (a) being modified        with one or more hydrophilic side groups.

Said polymer material may be any rubbery or elastomeric polymermaterial, e.g. one wherein said hydrophobic organic monomer (a) isselected from the group consisting of butadiene, isoprene,dialkylsiloxanes, diarylsiloxanes, acrylic acid alkyl esters,acrylonitrile, chloroprene, fluorinated ethylene, mixtures of ethyleneand vinyl acetate, mixtures of ethylene and one or more acrylic acidesters, and mixtures of ethylene with propylene and a diene.

In one embodiment of the present invention, a rubbery polymer materialmay be one wherein said hydrophobic organic monomer (a) is adialkylsiloxane or a diarylsiloxane, and wherein the total number ofrepeating units (a) and repeating units (b) is at least 5 and less than1,000.

In one embodiment of the present invention, said polymer material may beone wherein said hydrophilic side groups are ionic side groups such as,but not limited to, C3-C28 alkylsulfonate groups in association with acation. Said cation may be a monovalent cation selected from the groupconsisting of ammonium and alkali metal (Li, Na, K) cations, or adivalent cation selected from the group consisting of alkaline-earthmetal cations (Ca, Mg). Other hydrophilic side groups can also compriseat least one moiety from ionic groups such as sulfate (—OSO3-),phosphate (—OPO3 2-), phosponate (—PO3 2-), carboxylate (—CO2-),ammonium (NR1R2R3R4+), or phosphonium (PR1R2R3R4+) or combinations ofthese groups like in betaine (R1R2R3N+—CR4R5-CO2-) or sulfobetaine(R1R2R3N+—CR4R5-SO3-). It can also contain non ionic hydrophilic groupslike alcohol groups such as hydroxy (—OH), glycols (—OCH2CH2OH), orsugar derivates, ethers such as glycol ether (—(OCH2CH2-)nOR), amines(—NR1R2), amides (—CONR1R2), phosphine oxide (—POR1R2), aldehydes (—CHO)or esters (—COOR). Preferred counter ions comprise the before metionedammonium, alkali, earth alkali ions, H+ or mixtures and for the positivehydrophilic side chains the preferred counter ions are the halogenides(F—, Cl—, Br—, I—), hydroxide (OH—), acetate (CH3COO—), sulfite (SO32-),sulfate (SO42-), nitrite (NO2-), nitrate (NO3-), phosphate (PO43-),perchlorate (ClO4-) or tetrafluorborate (BF4-) or mixtures thereof.

In one embodiment of the present invention, said rubbery or elastomericpolymer material may be one wherein the repeating units (b) representfrom 1% to 30% for instance from 2% to 25%, or from 3% to 20%, or from5% to 15%, of the total number of repeating units (a) and repeatingunits (b). The proportion of repeating units (b) present in thewater-absorbing rubbery or elastomeric polymer material may beappropriately selected by the skilled person depending upon parameterssuch as, but not limited to, the type of repeating units (b), thedesired level and kinetics of water uptake, and the kind of medicaldevice or non-medical device, or part thereof, comprising said rubberyor elastomeric polymer material.

In one embodiment of the present invention, said rubbery or elastomericpolymer material may further comprise a detectable amount of a ligatingcompound or ligand. Said ligating compound or ligand may be a cycliccompound such as, but not limited to, a crown ether, a cryptand or acalixerene.

It is a principal object of other embodiments of the present inventionto provide a polymerizable composition suitable for producing a rubberyor elastomeric polymer material such as recited herein-above, saidcomposition comprising:

-   -   (a) one or more hydrophobic organic monomers or pre-polymers,    -   (b) one or more hydrophilic monomers capable of modifying said        hydrophobic organic monomers or pre-polymers (a) especially        under liquid phase polymerization conditions, being a C3-C28        alkenyl sulfonate in association with a cation, and    -   (c) a ligating compound or a solvent in an amount sufficient to        increase solubility or miscibility of said hydrophilic        monomers (b) in said hydrophobic organic monomers or        pre-polymers (a) under polymerization conditions.

The hydrophobic organic monomers or pre-polymers (a) may bebiocompatible in view of medicinal applications of the resultingpolymer.

In further embodiments of this invention, the hydrophilic monomer (b):

-   -   may react or associate with said ligating compound or solvent        (c),    -   after reaction or association with said ligating compound or        solvent (c), may be able to react with said hydrophobic organic        monomers or pre-polymers (a) under liquid phase polymerization        conditions, and/or    -   may be incorporated into the polymer sequence resulting from        liquid phase polymerization of said hydrophobic organic monomers        or pre-polymers (a).

The preferred polymerization method is the platinum-salt catalyzedmethod as this gives medical grade materials.

In one embodiment of the present invention, the hydrophilic side groupof said repeating units (b) may be an alkenyl sulphonate having from 3to 28 (preferably 10 to 18, more preferably 12 to 16) carbon atoms inassociation with a cation. Said cation may be a monovalent cationselected from the group consisting of ammonium and alkali metal cations(such as, but not limited to, the cations of Li, Na, or K). Said cationmay also be a divalent cation selected from the group consisting ofalkaline-earth metal cations (such as the cations of Ca or Mg).

In one embodiment of the present invention, the hydrophilic side groupof said repeating units (b) may be derived from a hydrophilic polymerselected from the group consisting of polyvinylpyrrolidones (usuallywith a number average molecular weight from 20,000 to 400,000),poly(hydroxyethyl methacrylates), polyethylene glycols (usually with anumber average molecular weight from 200 to 10,000), polyvinyl alcohols(usually with a number average molecular weight from 10,000 to 150,000),polyacrylamides, alkali metal poly(meth)acrylates (such as, but notlimited to, sodium polyacrylate, potassium polyacrylate, sodiumpolymethacrylate, potassium polymethacrylate), and mixtures thereof.

In one embodiment of the present invention, the polymer material may bea (partially) hydrophilic silicone-based rubber material wherein themolar ratio of the repeating units (a) to the repeating units (b) is atleast 4.5, preferably at least 7, more preferably at least 9, mostpreferably at least 13. In one embodiment of the present invention, thepolymer material may be a (partially) hydrophilic silicone-based rubbermaterial wherein the molar ratio of the repeating units (a) to therepeating units (b) is at most 90, preferably at most preferably 40,most preferably at most 25.

In one embodiment of the present invention, the (partially) hydrophilicsilicone-based rubber material may be a mixture of hydrophilic siliconerubber material and the hydrophilic molecule or polymer.

In one embodiment of the present invention, the (partially) hydrophilicsilicone-based rubber material has an exceptionally high water uptakecapacity, for instance it may take up more than 5% by weight (preferablymore than 10% by weight, more preferably more than 15% by weight, mostpreferably more than 20% by weight, of water after immersion indemineralized water at room temperature for a sufficient time such as 5days or more to reach saturation. The hydrophilic silicone-based rubbermaterial of the invention may take up at most 120% by weight, at most200% by weight, at most 250% by weight, or at most 500% by weight ofwater after immersion in demineralized water at room temperature for asufficient time such as 5 days or more to reach saturation (see FIG. 6).

In one embodiment of the present invention, the polymer material may bea (partially) hydrophilic silicone-based rubber material furthercomprising residual traces or detectable amounts of a ligating compoundor ligand that may be used during the process for its preparation. Forinstance when said hydrophilic side group is an alkenyl sulfonate havingfrom 3 to 28 (preferably 10 to 18, more preferably 12 to 16) carbonatoms in association with a cation, said compound may be a cyclic ligandsuch as, but not limited to, a crown ether, a cryptand or a calixarene.Although there are effective procedures for removing a ligand such as acrown ether or a cryptand from a hydrophilic silicone-based rubbermaterial of this invention, such as heating under vacuum, however it maybe unnecessary to completely remove said ligand and residual but stilldetectable traces of the ligand may be admissible for medicinalapplications. Methods for detecting and quantifying the presence ofligating compounds, such as crown ethers or cryptands, in a polymermaterial such as a (partially) hydrophilic silicone-based rubbermaterial of the present invention are well known to the person skilledin the art.

In further embodiments of the present invention are provided processesfor making the novel silicone-based rubber materials described herein.In one embodiment of the present invention, a first process forpreparing a hydrophilic silicone-based rubber material comprises thesteps of:

(a) providing a silicone precursor and one or more hydrophilic monomers(preferably a vinyl-terminated hydrophilic monomer) or polymers; and

(b) polymerizing said silicone precursor in the presence of saidhydrophilic monomers or polymers, until obtaining a hydrophilicsilicone-based rubber material which takes up more than 5% by weight(preferably more than 10% by weight, more preferably more than 15% byweight, most preferably more than 20% by weight) of water and at most upto 120% by weight of water, or up to 200% by weight of water, up 250% byweight of water, or 500% by weight of water after immersion indemineralized water at room temperature for a sufficient time such as 5days or more to reach saturation. vels.

In one embodiment of the present invention, a second process forpreparing a hydrophilic silicone-based rubber material comprises thesteps of:

(a) providing a silicone precursor and one or more hydrophilic ionicmonomers (preferably a vinyl-terminated hydrophilic ionic monomer) orpolymers;

(b) polymerizing said silicone precursor in the presence of saidhydrophilic ionic monomers or polymers and in the further presence of aligating compound or solvent.

In one embodiment of the present invention, a third process forpreparing a hydrophilic silicone-based rubber material comprises thesteps of:

(a) providing a silicone precursor having Si—O repeating units, whereinthe number of Si—O repeating units in said silicone precursor is atleast 5 and less than 1000,

(b) providing one or more hydrophilic monomers (preferably avinyl-terminated hydrophilic monomer) or polymers; and

(c) polymerizing said silicone precursor in the presence of saidhydrophilic monomers or polymers.

In one embodiment of each of the three above processes of the presentinvention, said silicone precursor may react with said hydrophilicmonomers (preferably a vinyl-terminated hydrophilic monomer) orpolymers. In particular said reaction may be via addition of a vinylgroup onto a silicon-hydrogen bond.

In one embodiment of each of the three above processes of the presentinvention, said silicone precursor bears reactive Si—H groups with aspacer group between said reactive Si—H groups, which preferablycomprises at least 5 and less than 1,000 silicon atoms interspersed withoxygen atoms.

In one embodiment of each of the three above processes of the presentinvention, said hydrophilic monomer may be an alpha-olefin or alkenylsulfonate having 3 to 28 (preferably 10 to 18, more preferably 12 to 16)carbon atoms in association with a cation. Said cation may be amonovalent cation selected from the group consisting of ammonium andalkali metal cations (such as, but not limited to, the cations of Li,Na, or K). Said cation may also be a divalent cation selected from thegroup consisting of alkaline-earth metal cations (such as the cations ofCa or Mg).

Other hydrophilic side groups can also comprise at least one moiety fromionic groups such as sulfate (—OSO3-), phosphate (—OPO3 2-), phosponate(—PO3 2-), carboxylate (—CO2-), ammonium (NR1R2R3R4+), or phosphonium(PR1R2R3R4+) or combinations of these groups like in betaine(R1R2R3N+—CR4R5-CO2-) or sulfobetaine (R1R2R3N+—CR4R5-SO3-). It can alsocontain non ionic hydrophilic groups like alcohol groups such as hydroxy(—OH), glycols (—OCH2CH2OH), or sugar derivates, ethers such as glycolether (—(OCH2CH2-)nOR), amines (—NR1R2), amides (—CONR1R2), phosphineoxide (—POR1R2), aldehydes (—CHO) or esters (—COOR). Preferred counterions comprise the before metioned ammonium, alkali, earth alkali ions,H+ or mixtures and for the positive hydrophilic side chains thepreferred counter ions are the halogenides (F—, Cl—, Br—, I—), hydroxide(OH—), acetate (CH3COO—), sulfite (SO32-), sulfate (SO42-), nitrite(NO2-), nitrate (NO3-), phosphate (PO43-), perchlorate (ClO4-) ortetrafluorborate (BF4-), or mixtures thereof.

In one embodiment of each of the three above processes of the presentinvention, said hydrophilic polymer may be selected from the groupconsisting of polyvinylpyrrolidones (usually with a number averagemolecular weight from 20,000 to 400,000), poly(hydroxyethylmethacrylates), polyethylene glycols (usually with a number averagemolecular weight from 200 to 10,000), polyvinyl alcohols (usually with anumber average molecular weight from 10,000 to 150,000),polyacrylamides, alkali metal poly(meth)acrylates (such as, but notlimited to, sodium polyacrylate, potassium polyacrylate, sodiumpolymethacrylate, potassium polymethacrylate), and mixtures thereof.

In one embodiment of each of the three above processes of the presentinvention, said silicone precursor reacts with said hydrophilic monomeror polymer in the presence of a ligating compound or a solvent. Theligating compound may be a cyclic ligating compound such as, but notlimited to, a crown ether, a cryptand or a calixarene, for instance acrown ether capable of dissolving the cation associated with thealpha-olefin or alkenyl sulfonate having 3 to 28 (preferably 10 to 18,more preferably 12 to 16) carbon atoms.

A suitable crown ether may depend upon the atomic size of the cation. Inone embodiment of the present invention, the cation is a lithium ion andthe crown ether is a 12-crown-4 crown ether. In one embodiment of thepresent invention, the cation is a sodium ion and the crown ether is a15-crown-5 crown ether. In one embodiment of the present invention, thecation is a potassium ion and the crown ether is a 18-crown-6 crownether.

In place of a ligating compound, a solvent may be used to assistdissolution of the alkenyl sulfonate into the siloxane precursor. In oneembodiment of the present invention, the solvent has a very low boilingpoint below 100° C. In another embodiment of the present invention, thesolvent may be a ketone (such as, but not limited to, acetone), anotherpolar solvent (such as, but not limited to, chloroform), a low boilingalcohol (such as, but not limited to, ethanol) or a mixture of said lowboiling alcohol with water. In another embodiment of the presentinvention, the solvent may have a higher boiling point, for instancebetween 100° C. and 300° C., to provide a more stable mixture during thetotal production process. This higher boiling solvent can be analiphatic alcohol such as, but not limited to, isopropanol, hexanol ordecylalcohol, an aliphatic ether such as, but not limited to, anethylene- or propylene-glycol ether or di- and trimers of ethylene orpropylene glycol, a ketone such as, but not limited to, methylethylketone, methylpropyl ketone or cyclohexanone, a chlorinated solvent suchas, but not limited to, trichloroethylene, tetrachloroethylene or(di)chlorobenzene or any other polar solvent.

In one embodiment of each of the three above processes of the presentinvention, the hydrophilic silicone-based rubber material comprises atleast one material represented by the following structural formula:

R═Si(CH₃)₃ or H

wherein n is from 3 to 28 (preferably 10 to 18, more preferably 12 to16) and wherein the total number (m+o+1) of repeating units is at least5 and less than 1,000, with n and o being integers independentlyselected from each other and preferably being at least 6. In the abovestructural formula, the terminal end groups R usually consist ofSi(CH3)3 and/or hydrogen.

In one embodiment of the present invention, the hydrophilicsilicone-based rubber material comprises at least one materialrepresented by the above structural formula, wherein the molar ratio m/ois at least 4.5, preferably at least 7, more preferably at least 9, mostpreferably at least 13. In one embodiment of the present invention, thehydrophilic silicone-based rubber material comprises at least onematerial represented by the above structural formula, wherein the molarratio m/o is at most 90, preferably at most preferably 40, mostpreferably at most 25.

In one embodiment of the present invention, a hydrophilic siliconematerial comprises a silicone precursor material, a sodium alpha-olefinsulfonate, and a crown ether mixing mediator that facilitates mixing ofthe sodium alpha-olefin sulfonate with the silicone precursor material.The silicone precursor material may be a commercial silicone elastomermaterial such as, but not limited to, Elastosil LR 3004/40 from WackerSilicones (Germany). The sodium alpha-olefin sulfonate is also acommercially available product, or may be produced according to methodswell known in the art. The crown ether may be a 15-crown-5 ether. In oneembodiment of the present invention, the hydrophilic silicone materialincludes from 40 to 98.5% by weight of the silicone precursor material,from 1 to 30% by weight of the sodium alpha-olefin sulfonate, and up to30% by weight of the mixing mediator, and it takes up from 1 to 85% byweight of water after immersion in demineralized water for 5 days atroom temperature.

In a further embodiment of the present invention, a method formanufacturing a hydrophilic silicone material includes the steps of:mixing a sodium alpha-olefin sulfonate with an a component of a siliconeprecursor material and with a crown ether or solvent mixing mediator,adding a silicone precursor B component, mixing again, and obtaining ahydrophilic silicone mixture. The method for manufacturing a hydrophilicsilicone material includes standard production techniques with steps:casting or molding the hydrophilic silicone mixture, curing thehydrophilic silicone mixture, and obtaining the hydrophilic siliconematerial. The method for manufacturing a hydrophilic silicone materialincludes further the steps of: mixing the sodium alpha-olefin sulfonatewith silicone precursor material and with the mixing mediator. Alsomixing of hydrophilic silicone and sodium alpha-olefin without mediatoris possible. The method for manufacturing a hydrophilic siliconematerial includes further the steps of: providing a commercial sodiumalpha-olefin sulfonate, providing a commercial silicone elastomer as thesilicone precursor material, and providing a 15-crown-5 ether as themixing mediator. The method for manufacturing a hydrophilic siliconematerial includes further the step of performing the mixing at roomtemperature.

In a more general aspect, the present invention provides a process forpreparing a rubbery or elastomeric polymer material, comprising thesteps of:

-   -   providing one or more hydrophobic organic monomers,    -   providing one or more hydrophilic monomers or polymers, and    -   polymerizing said hydrophobic organic monomers in the presence        of said hydrophilic monomers or polymers until obtaining a        rubbery or elastomeric polymer material wherein repeating units        from the one or more hydrophobic organic monomers are modified        with hydrophilic groups from said one or more hydrophilic        monomers or polymers, said rubbery or elastomeric polymer        material taking up more than 5% by weight of water and at most        120% by weight of water, up to 200%, up to 250% or up to 500%        weight of water after immersion in demineralized water at room        temperature for a sufficient time, such as 5 days or more, to        reach saturation.

In a further embodiment of this general method of the present invention,polymerization occurs in the presence of a ligating compound or asolvent for said hydrophilic monomer or polymer. In one embodiment ofthe present invention said ligating compound is a crown ether, acryptand or a calixarene such as described herein-above. In oneembodiment of the present invention, the solvent has a very low boilingpoint. In another embodiment of the present invention, the solvent maybe a ketone (such as, but not limited to, acetone), another polarsolvent (such as, but not limited to, chloroform), a low boiling alcohol(such as, but not limited to, ethanol) or a mixture of said low boilingalcohol with water. In another embodiment of the present invention, thesolvent may have a higher boiling point, for instance between 100° C.and 300° C., to provide a more stable mixture during the totalproduction process. This higher boiling solvent can be an aliphaticalcohol such as, but not limited to, isopropanol, hexanol ordecylalcohol, an aliphatic ether such as, but not limited to, anethylene- or propylene-glycol ether or di- and trimers of ethylene orpropylene glycol, an aliphatic ketone such as, but not limited to,methyl ethyl ketone, methyl propyl ketone or cyclohexanone, achlorinated solvent such as, but not limited to, trichloroethylene,tetrachloroethylene or (di)chlorobenzene or any another polar solvent.

In a still further embodiment of the present invention, the hydrophilicsilicone material is used in a material system in combination with ahydrophobic silicone base material. At least a part of the hydrophilicmaterial is in contact with a moist surface. The hydrophobic basematerial provides mechanical and dynamical stability of the materialsystem. The hydrophilic material allows for uptake of moisture anddiffusion of moisture away from the moist surface. The moist surface maybe skin of a person. In one embodiment of the invention, the hydrophobicbase material forms a base layer and the hydrophilic material forms atop layer placed above the base layer. In another embodiment of thepresent invention, the hydrophilic material is mixed into thehydrophobic base material to form a composite mixture, a layer ofhydrophobic base material is formed at an outside of the compositemixture, the layer is perforated forming apertures, and the aperturesconnect the hydrophilic material with the moist surface. In stillanother embodiment of the invention, the hydrophobic base materialincludes a plurality of holes positioned at an interface of thehydrophobic base material with the moist surface, the holes are filledwith the hydrophilic material, and the hydrophilic material is incontact with the moist surface.

In a still further embodiment of the present invention, the materialsystem is utilized to fabricate a skin-contact product such as, but notlimited to, a patient interface material of a patient interface device.The moist surface is skin of a person wearing the face mask. The maskmaterial can be, for example, integrated in a patient interface mask forpositive air pressure therapy of obstructive sleep apnea. Thehydrophobic silicone base material provides mechanical and dynamicalstability of the patient interface device and the hydrophilic siliconematerial allows for uptake and diffusion of moisture away from a patientinterface device-skin interface. The patient interface material reducesmoisture accumulation, stratum corneum hyper-hydration and thuscontributes to tissue tolerance to shear stress and thus to less damageof the skin for example during wearing a patient interface device. Theskin contract product thus improves comfort of a patient interfacedevice and supports the reduction of red mark formation and skinirritation for example if a patient interface mask is applied to theskin.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will now be described, by way of example, withreference to the accompanying drawings, in which:

FIG. 1 is a schematic cross-sectional view of a material system withdefined layers of hydrophilic and hydrophobic silicone materials inaccordance with one embodiment of the present invention;

FIG. 2 is a schematic cross-sectional view of a material system with atwo phase compound of hydrophilic and hydrophobic silicone materials inaccordance with another embodiment of the present invention;

FIG. 3 is a schematic cross-sectional view of a material system with ahorizontally stacked configuration of hydrophobic and hydrophilicmaterials in accordance with still another embodiment of the presentinvention;

FIGS. 4 a and 4 b is a perspective view of an exemplary patientinterface device or face mask in accordance with the various embodimentsof the present invention;

FIG. 5 shows moisture generation by various materials that can be usedwith the present invention;

FIG. 6 shows moisture uptake for various materials that can be used withthe present invention;

FIGS. 7 and 8 show the water uptake of different hydrophilic siliconerubber materials (wherein the term “soap” is used as an abbreviation todesignate sodium sulfonate groups) as a function of time, in comparisonwith a hydrophobic silicone rubber material without alkylsulfonategroups; and

FIG. 9 shows an exemplary user or patient interface that can be usedwith the present invention.

Corresponding reference characters indicate corresponding partsthroughout the several views. The exemplification set out hereinillustrates exemplary embodiments of the invention, in one form, andsuch exemplification is not to be construed as limiting the scope of theinvention in any manner.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS 1. Definitions

Hydrophobic materials are characterized by a water contact angle that islarger than that of hydrophilic materials. The larger the contact angle,the more hydrophobic is the material, the smaller the contact angle, themore hydrophilic is the material. Hydrophilic materials are definedherein as materials that allow the uptake and/or diffusion of water.

Examples of hydrophobic materials are silicone rubbers, natural rubbers,polyalkene polymers like polyethylene and polypropylene,fluorine-containing polymers like Teflon, oils, waxes etc. In thecontext of the various embodiments of the present invention, preferredhydrophobic materials are hydrophobic silicones and natural rubbers.

Examples of hydrophilic materials are natural fabrics like cotton, silkor wool, hydrogels as used in contact lenses or diapers, water solublepolymers like polyvinylalcohol, polyethylene glycols, natural polymerslike proteins (gelatin) or polysaccharides (agar agar, mucins) andhygroscopic inorganic compounds like zeolites, zeolite based componentsor salts. In the context of the various embodiments of the presentinvention, preferred hydrophilic materials are hydrophilic silicones,with a crosslinking structure and/or crosslinking density comparable tothat of suitable hydrophobic materials, which may be combined in asingle composite material. Hydrophilic silicones have a normal siliconebackbone but instead of hydrophobic methyl or phenyl groups some ofthese groups are exchanged for more hydrophilic side groups. Hydrophilicside groups contain, for example, alcohol, carboxylic acid, amine, amideand ethylene glycol functional groups.

The present invention will be described with respect to particularembodiments and with reference to certain drawings but the invention isnot limited thereto but only by the claims. The drawings described areonly schematic and are non-limiting. In the drawings, the size of someof the elements may be exaggerated and not drawn on scale forillustrative purposes. Where an indefinite or definite article is usedwhen referring to a singular noun e.g. “a” or “an”, “the”, this includesa plural of that noun unless something else is specifically stated.

The term “comprising”, used in the claims, should not be interpreted asbeing restricted to the means listed thereafter; it does not excludeother elements or steps. Thus, the scope of the expression “a devicecomprising means A and B” should not be limited to devices consistingonly of components A and B. It means that with respect to the presentinvention, the only relevant components of the device are A and B.

Furthermore, the terms first, second, third and the like in thedescription and in the claims, are used for distinguishing betweensimilar elements and not necessarily for describing a sequential orchronological order. It is to be understood that the terms so used areinterchangeable under appropriate circumstances and that the embodimentsof the invention described herein are capable of operation in othersequences than described or illustrated herein.

Moreover, the terms top, bottom, over, under and the like in thedescription and the claims are used for descriptive purposes and notnecessarily for describing relative positions. It is to be understoodthat the terms so used are interchangeable under appropriatecircumstances and that the embodiments of the invention described hereinare capable of operation in other orientations than described orillustrated herein.

The present invention relates to skin-contact products with moisture andmicroclimate control such as medical devices or medicinal products,especially patient interface devices of which face masks, aspirators,ventilators, breast pumps or wound dressings are examples and, moreparticularly, to a skin-contact product with moisture and microclimatecontrol with an improved microclimate at a skin interface. The inventionwill mainly be described with reference to a user or patient interfacedevice, such as a face mask, as this medical application involves thebasic elements of the present invention:

-   -   a) contact with the skin over a period of time, e.g. several        hours,    -   b) pressure areas on the skin,    -   c) a material in direct contact with the skin,    -   d) formation of a microclimate on areas of the skin,    -   e) a requirement of at least a transpiration function, i.e.        sweat or moisture from the skin must be allowed to migrate from        the skin, and    -   f) Gaseous materials may need to be communicated or exchanged        through a material part of the device such as air or oxygen for        breathing or air or oxygen in a wound dressing. Other gases may        be communicated for special uses, e.g. anesthetics.

These characteristics are common to user interface devices such asrespiratory masks used by firefighters, patient interface devices, suchas respiratory masks, face masks, breast pumps or wound dressings orother health care products.

The skin-contact product may include an enclosure or shell such as istypical for a user or patient interface device or mask. A user orpatient interface device may include a mask shell having a contactportion or cushion attached to the shell that contacts the surface ofthe patient. The mask shell and cushion are typically held in place by aheadgear that wraps around the head of the patient or person. The maskand headgear form the user or patient interface assembly. A typicalheadgear includes flexible, adjustable straps that extend from the maskto attach the mask to the patient or person.

The enclosure or shell can be made of rigid material or of a semi-rigidmaterial e.g. a flexible material that is sufficiently form stable. Anexample is polycarbonate plastic. Such an enclosure or shell can have arim that forms a seal with the skin at its rim, e.g. a seal such asrequired for aspiration, ventilation etc. of a person when using a useror patient interface device. such as a mask or can be for theapplication of vacuum in a wound dressing. For example, a flap canextend around a rim or perimeter of the patient interface device and canbe made of a relatively flexible material to provide a leak resistantseal over the patient contacting area.

Because such patient interface devices can be worn for an extendedperiod of time, a variety of concerns must be taken into consideration.For example, in some treatments, the person or patient wears the user orpatient interface device all day when they work (e.g. a firefighter) orall night long while he or she sleeps. One concern in such a situationis that the patient interface device is as comfortable as possible,otherwise the patient may avoid wearing the interface device, defeatingthe purpose, e.g. to protect against fumes or to provide the prescribedpressure support therapy. When used facially, it is also important thatthe interface device provide a tight enough seal against a user's orpatient's face without discomfort. A problem arises in that in order forthe user or patient interface device to maintain a seal without anyundue gas leaks around its periphery, the patient interface device maybe compressed against the patient's face.

Accordingly and referring to FIG. 9 , there is generally indicated at100, a user interface device such as a patient interface device whichcan be used with the present invention including a body or shell 112having a first side that defines a generally annular surface to which issealingly coupled a cushion 118. Shell 112 is preferably, although notnecessarily, a generally rigid shell, and can be transparent whereascushion 118, in the illustrated embodiment, is a flexible, resilientmember that will be described in greater detail hereinafter. Cushion 118according to embodiments of the present invention comprises a supportmaterial 132, and a contact structure 134 comprising moisture uptakemeans that is non-releasably combined with and supported by the supportmaterial 132, wherein the contact structure 134 is adapted so that themoisture uptake means at least partially contacts a skin surface of auser responsive to the user interface being worn by such a user whereinthe support material provides mechanical and dynamical stability for themoisture uptake means, or the first portion of the user contactassembly, and wherein the moisture uptake means allows for uptake ordiffusion of moisture from a skin surface of a user over which thecontacting assembly is disposed.

Shell 112 also defines an opening 120 to which, in the illustratedembodiment, there is connected a fluid coupling device such as a gastransfer port, e.g. a swivel coupling 121 for carrying fluid, such as abreathing gas, between a chamber within the mask and an external gassource. It is to be understood that with the present invention a varietyof fluid coupling devices can be attachable, either permanently orselectively, to opening 120 to carry fluid to or from the chamberdefined by user or patient interface device 100. In the illustratedembodiment, opening 120 and intervening coupling 121 connect user orpatient interface device 100 via a conduit, which is represented by line122, to a source of gas 124, e. g., a blower or other suitable device,for providing a flow of pressurized breathing gas, for example, foradministration of the gas to a user. Coupling 121 preferably includesexhaust vents which exhaust exhaled gases in a known manner. The presentinvention contemplates that an exhaust vent can be any conventionalexhaust vent, and can be located on the mask, such as on the mask shell,on the patient circuit, at the mask shell/patient circuit interface, orat any combination of such locations. The exhaust vent can be asdescribed in published U.S. application Ser. No. 10/119,673, entitled,“Exhaust Port Assembly for a Pressure Support System,” Publication No.US 2003 0005931, the contents of which are incorporated herein byreference.

In the illustrated embodiment, cushion 118 is preferably attached toshell 112 using ring 126 in a known manner. The cushion may include afirst end portion that couples to the mask shell. The first end portioncan be generally triangular shaped and attaches to similarly-shapedopening provided in a second side of the mask shell. The mask shell andthe first end portion of the seal that attaches thereto can be bothgenerally planer, i.e., both lies in a linear plane. It should be notedthat the present invention contemplates that the mask shell and thefirst end portion of the seal can be contoured, when viewed in profile,so that first end portion, for example, does not lie in a common plane.

It is to be further understood that the present invention contemplatesusing any conventional technique for attaching the first end portion ofthe cushion to the mask shell. Such techniques include permanentlybonding the cushion to the mask shell, for example, using adhesives,mechanical fasteners, or molding the cushion onto the shell such thatthe cushion is selectively detachable from the mask shell. When coupledto the mask shell, the cushion can define a chamber for receiving aportion of the user or patient when the mask is donned by the user orpatient. Typically, a part of the user or patient, such as the user's orpatient's nose, inserts into the chamber so that the user's or patient'sairway is in fluid communication with the chamber.

The cushion can include a second end portion for sealing engagement witha face of a patient. A sidewall can be provided that extends betweenfirst end portion and second end portion. The cushion can be a unitarystructure that attaches to a mounting portion of a mask shell or othersupport structure and provides a surface at second end portion thatcontacts a surface of a patient. In the case of a nasal mask, forexample, the second end portion contacts the area of the user or patientgenerally around the nose including over the bridge of the nose.

Source of gas 124 is any device that provides gas to the user. The gassource may include an oxygen supply, a ventilator, a pressure supportdevice, such as a CPAP device, a variable pressure device, e.g., aBiPAP®, Bi-Flex, or C-Flex device manufactured and distributed byRespironics, Inc. of Pittsburgh, Pa., or an auto-titration pressuresupport system. A BiPAP, Bi-Flex, or C-Flex device is a pressure supportdevice in which the pressure provided to the patient varies with thepatient's respiratory cycle, so that a higher pressure is deliveredduring inspiration than during expiration. An auto-titration pressuresupport system is a system in which the pressure varies with thecondition of the patient, such as whether the patient is snoring orexperiencing an apnea, hypopnea, flow limited breathing, upper airwayresistance, or snoring.

The user or patient interface device 100 shown is a full or anoral/nasal mask that accommodates both the mouth and nasal regions ofthe user's face. It is to be understood, however, that the presentinvention also contemplates a nasal mask that accommodates both thenasal regions of a user or a total face mask that accommodatessubstantially the entire facial area of the patient. It should also beunderstood that the illustrated embodiments are examples only of masksusing the materials of the present invention and that the presentinvention is not limited to the embodiments described herein.Embodiments of the present invention include a respiratory maskincluding a shell and seal, can have any one of an infinite number ofconfigurations, shapes, and sizes. The shell can correspond to thatdescribed in U.S. application Ser. No. 10/654,379, entitled, “PatientInterface With Forehead Support System,” the contents of which areincorporated herein by reference. The mask shell is preferably formedfrom rigid plastic, such as polycarbonate. As described in detail in the'379 application the mask can include an adjustable forehead support.

The forehead support can be generally T-shaped and can include a supportarm, which is slideably connected to a forehead support bracket. Theforehead support bracket includes a forehead pad disposed on the patientcontacting side to engage the forehead of the user. It is to beunderstood that the present invention contemplates that the foreheadsupport assembly, and its individual components, can have anyone of avariety of configurations. The present invention also contemplates thatthe forehead support assembly can be eliminated entirely.

A headgear can be used to attach to the mask via headgear clips.Headgear clips can attach to headgear straps, for example by insertingthe headgear straps into slots provided on the clips. The headgear clipsare selectively attachable to the mask shell in any conventional manner.The headgear clips attach to each side of forehead support bracket andto each side of the lower portion of the mask shell. It can thus beappreciated that the headgear and head clip can have any configurationso as to be selectively attachable to the mask. It is to be furtherunderstood that the present invention contemplates eliminating all, or aportion, of the headgear clips an attaching the headgear straps to themask shell. For example, in the illustrated embodiment, the lowercorners of shell 112 also include headgear attaching elements in theform of receiving socket attachment elements 125 which cooperate withcorresponding ball elements (not illustrated) on headgear straps. Theball and socket configuration, and other headgear attachmentconfigurations suitable for use with the present invention, aredisclosed in co-pending U.S. patent application Ser. No. 10/629,366,(publication no. US-2004-0025883-A1) the contents of which areincorporated herein by reference. It is to be understood, however, thatthe present invention contemplates using any conventional connectionassemblies to attach a headgear to mask shell 112 in this or any of theother embodiments.

The present invention contemplates the headgear 119 that can be usedwith user or patient interface device 100 can be any suitable headgear,i.e., any conventional headgear used in the user or patient interfacefield. For example, a typical headgear assembly comprises a headpiecethat overlies a portion of the user or patient's crania and withheadgear straps extending therefrom to adjustably connect the headgearto the mask.

Referring now to FIG. 1 , material for a contact structure comprisingmoisture uptake means that is non-releasably combined with and supportedby a support material will be described. A material system 10 withdefined layers of hydrophilic and hydrophobic materials is illustratedin accordance with one embodiment of the present invention. Thematerials in embodiments of the present invention are preferablyhydrophilic and hydrophobic silicone materials. Alternative hydrophilicmaterials are for example polyurethanes but also moisture uptakingtextiles such as cotton, silk or polyester with defined structure orhydrophobic textiles with hydrophilic coating. Alternative hydrophobicmaterials are latex or polybutadien.

Preferably a rubber or elastomeric material is used to provide asufficient seal. At this moment there only a few rubber materialscommercially available: natural rubber (latex), silicone rubber, rubbersbased on butadiene or butadiene containing compounds (examples areisoprene, halogenated butadiene and mixtures with butadiene (nitrilerubber, styrene rubber)) and special rubbers like perfluorinated rubbers(Viton) and acrylate rubbers. Silicone rubbers are preferred as they arevery compatible with the skin and can be molded in any form.

Hydrophilic polyurethanes are made by coupling the diisocyanate monomeror pre-polymer with hydrophilic monomers or pre-polymers. Examples ofhydrophilic monomers or pre-polymers are glycerol, ethylene glycolderivatives, polyethylene glycol and other hydroxyl function containingpoly-ol compounds. The hydrophilic properties can be even furtherincreased by coupling this small chain hydrophilic polyurethane withother hydrophilic polymers which do not necessarily contains a hydroxylgroup. Examples of these more general hydrophilic polymers are:polyvinylpyrrolidones (usually with a number average molecular weightfrom 20,000 to 400,000), poly(hydroxyethyl methacrylates), polyethyleneglycols (usually with a number average molecular weight from 200 to10,000), polyvinyl alcohols (usually with a number average molecularweight from 10,000 to 150,000), polyacrylamides, alkali metalpoly(meth)acrylates (such as, but not limited to, sodium polyacrylate,potassium polyacrylate, sodium polymethacrylate, potassiumpolymethacrylate), and mixtures thereof.

In embodiments of the present invention a user contacting assembly isprovided having a first portion comprising:

-   -   (a) a support material, and    -   (b) a contact structure comprising moisture uptake means that is        non-releasably combined with and supported by the support        material, wherein the contact structure is adapted so that the        moisture uptake means at least partially contacts a skin surface        of a user responsive to the user interface being worn by such a        user wherein the support material provides mechanical and        dynamical stability for the moisture uptake means, and wherein        the moisture uptake means allows for uptake or diffusion of        moisture from a skin surface of a user over which the patient        contacting assembly is disposed.

In the following a selection of embodiments are described to illustrateaspects of the present invention but these are only examples and theskilled person will realise that alternatives thereto are includedwithin the scope of the present invention. The embodiments providevarious material systems that comprise a plurality of materials which incombination provide the support material, and the contact structure.

In particular in one embodiment a material system 10 includes ahydrophobic material base layer 11 and a hydrophilic material top layer12. Hydrophilic material top layer 12 is in contact with a moistsurface, such as skin 50. Hydrophilic material top layer 12 comprises orconsists of intrinsically hydrophilic material. The stiffness ofhydrophilic materials can depend strongly on the water content.Typically, hydrophilic materials exhibit lower stiffness at higher watercontent. High water content occurs for for hydrophilic materials whichshow a good water permeability. Therefore, hydrophilic material toplayer 12 may be combined with hydrophobic material base layer 11 byplacing layer 12 on top of layer 11. Thus, layer 12 may allow forpenetration or uptake of moisture from skin 50 by utilizing thehydrophilic nature of the polymers molecular framework or by allowingfor passage of moisture through the material through dedicated-channels.Accordingly, moisture accumulation in skin 50 may be prevented.

Material system 10 may be, for example, utilized to fabricate aninterface material such as a user or patient interface device materialsuch as a cushion 41 and a forehead pad 42 or any other material in themask in contact with the skin of a user interface or patient interfacedevice 40, as illustrated in FIG. 4 a . The user interface, and,therefore, face mask 40, may be, but is not limited to, a PAP patientinterface mask. Other applications for material system 10 may include,for example, respiratory patient interface devices, gas masks,pressurized masks, or diving masks. Skin 50 may be the skin of a person,such as a patient receiving PAP treatment, wearing face mask 40. Thepatient interface device or mask material 41 may be made in a standardway but also any technology to realize the patient interface devicesmaterial can be used. However, instead of filling a mold completely withhydrophobic injection molding material as done in the prior art, themold may be filled with base layer 11 of a hydrophobic material, such asa hydrophobic silicone material, and a top layer 12 of a hydrophilicmaterial, such as a water free hydrophilic silicone material. Top layer12 may be preferably positioned at a patient interface devicematerial-skin interface 43 that comes in contact with skin 50 when apatient interface device 40 is worn by a person.

Accordingly, a face mask 40, such as a PAP patient interface device,with a standard stiffness and a water absorbing and water permeablepatient interface material-skin interface 43 may be fabricated utilizingmaterial system 10 in accordance with an embodiment of the presentinvention.

For example, a flap can extend around a rim or perimeter of the patientinterface device and can be made of a relatively flexible material toprovide a leak resistant seal over the patient contacting area.Alternatively, by utilizing material system 10 an airtight seal may beformed at material-skin contact area 43 allowing for the use ofoverpressure. An example of such a face mask with a hydrophilic siliconelayer 12 processed on top of a hydrophobic silicone part 11 bycompression molding is shown in FIG. 4 b.

The stiffness of face mask 40 provided by hydrophobic material baselayer 11 may be such that patient interface 40 withstands theoverpressure. An improved microclimate at mask material-skin contactarea 43 may be provided by hydrophilic material top layer 12.

Referring now to FIG. 2 , material system 20 with a two phase compoundof hydrophilic and hydrophobic materials is illustrated in accordancewith one embodiment of the present invention. Material system 20includes a hydrophobic base material 21 and hydrophilic material 22mixed into hydrophobic base material 21. The outside of material system20 may be formed of hydrophobic base material 21, which may beperforated to include apertures 24. Apertures 24 may connect hydrophilicmaterial 22 with a moist surface, such as skin 50. Material system 20may by a composite mixture, where at least one hydrophilic material 22is combined with at least one hydrophobic base material 21. Hydrophilicmaterial 22 may allow for uptake and/or diffusion of moisture away fromthe interface of material system 20 with skin 50. Hydrophobic basematerial 21 may provide the mechanical and dynamical stability ofmaterial system 20.

Material system 20 may be, for example, utilized to fabricate a user orpatient interface cushion, such as a cushion 41 and a forehead pad 42 ofa user interface or patient interface, such as face mask 40, asillustrated in FIG. 4 . The user interface, and, therefore, face mask 40may be, but is not limited to, a PAP patient interface mask. Otherapplications for material system 20 may include, for example,respiratory masks, gas masks, pressurized masks, or diving masks. Skin50 may be the skin of a person, such as a patient receiving PAPtreatment, wearing face mask 40. Patient interface device cushion 41 maybe made from a composite mixture of hydrophobic base material 21, suchas a hydrophobic silicone material, and hydrophilic material 22, such asa water free hydrophilic silicone material. The ratio between thehydrophobic base material 21 and the hydrophilic material 22 may bechosen such that mask 40 has the required stiffness. The components ofmaterial system 20 may phase separate during crosslinking to form awater-absorbing and a water-repelling phase. The outer surface of maskcushion 41 or forehead pad 42 may be covered with a layer 211 ofhydrophobic base material 21 as these have the lowest surface energy.Afterwards, layer 211 may be perforated to form apertures 24 that enablewater absorption from skin 50 in the hydrophilic material 22.

In this embodiment of a composite material of hydrophilic andhydrophobic the layer 211 is optional.

By utilizing material system 20 in accordance with an embodiment of thepresent invention, an airtight seal may be formed at patient interfacematerial skin contact area 43 allowing for the use of overpressure. Thestiffness of face mask 40 provided by hydrophobic base material 21 maybe such that face mask 40 withstands the overpressure. An improvedmicroclimate at patient interface material-skin contact area 43 may beprovided by hydrophilic material 22.

Referring now to FIG. 3 , a material system 30 with a horizontallystacked configuration of hydrophobic and hydrophilic materials isillustrated in accordance with one embodiment of the present invention.Material system 30 includes a hydrophobic base material 31 that includesa plurality of holes 34 positioned at an interface 35 of hydrophobicbase material 31 with a moist surface, such as skin 50, and ahydrophilic material 32 filling holes 34. As can be seen in FIG. 3 , thehydrophilic material 32 may come in contact with skin 50 and, thus, incontact with moisture. Hydrophilic material 32 may accordingly allow foruptake and/or diffusion of moisture away from the contact area ofmaterial system 30 with skin 50. Hydrophobic base material 31 mayprovide the mechanical and dynamical stability of material system 30.

Material system 30 may be, for example, utilized to fabricate aninterface material, such as a cushion 41 and a forehead pad 42 of a userinterface or patient interface, such as face mask 40, as illustrated inFIG. 4 a . The user interface, and, therefore, face mask 40 may be, butis not limited to, a PAP patient interface. Other applications formaterial system 30 may include, for example, respiratory masks, gasmasks, pressurized masks, or diving masks. Skin 50 may be the skin of aperson, such as a patient receiving PAP treatment, wearing patientinterface 40. Patient interface material 41 may be made in a standardway. However, a mold for patient interface material 41 may be adapted tohave small indentations in the patient interface material-face contact43 area. The mold may be filled with hydrophobic base material 31, suchas a hydrophobic silicone material, whereby the indentations of the moldform holes 34. Holes 34 may be filled with a hydrophilic material 32,such as a water free hydrophilic silicone material. If the crosslinkingreaction of both silicone materials 31 and 32 is similar and if thecrosslinking of hydrophobic base material 31 is not fully complete,hydrophilic material 32 may react with hydrophobic base material 31 anda relatively strong adhesion between the two phases of the materials 31and 32 may result. If the crosslinking in hydrophobic base material 31is already complete, such adhesion may be supported by a plasmatreatment.

By utilizing material system 30 as in an embodiment of the presentinvention, an airtight seal may be formed at patient interface-skincontact area 43 allowing for the use of overpressure. The stiffness ofpatient interface 40 provided by hydrophobic base material 31 may besuch that patient interface 40 withstands the overpressure. An improvedmicroclimate at patient interface-skin contact area 43 may be providedby hydrophilic material 32.

By providing material systems 10, 20, and 30 in accordance with variousembodiments of the present invention, an improved microclimate at userinterface or a patient interface, such as material-face contact area 43of a patient interface 40 may be created by utilizing various materialarrangements, such as layered, mixed, or stacked, of hydrophobic basematerials 11, 21, and 31, respectively, and hydrophilic materials 12,22, and 32, respectively, for the fabrication of mask cushion 41 andforehead pad 42. As a result, a user interface, such as face mask 40,with a sufficient stiffness and a water absorbing and water permeablemask cushion-skin interface 43 may be fabricated in accordance with oneembodiment of the present invention. Accordingly, accumulation ofmoisture at the material skin interface or stratum corneumhyper-hydration of skin 50 may be reduced.

The moisture accumulation (given in arbitrary units) if a standardhydrophobic silicone is applied to the skin and a strong reduction ofmoisture accumulation at the skin is given in FIG. 5 if a hydrophilicsilicone is used in contact with the skin.

FIG. 6 shows the moisture accumulation at the skin with standardhydrophobic silicones and with textiles such as silk or cotton. A strongreduction of moisture accumulation is obtained if textiles are used incontact with the skin.

The material thus contributes to less moisture accumulation in the skinand increases the tissue tolerance to shear stress and friction and thusto less damage of the skin for example during wearing a patientinterface device. The skin contract product thus improves comfort of apatient interface device and supports the reduction of red markformation, skin irritation, skin damage for example if a patientinterface mask is applied to the skin.

In a further embodiment in accordance with the present invention, anovel composition for the preparation of hydrophilic silicone materialssuitable for application, for example, in material systems 10, 20, and30, as described above, is provided. The composition may enable improvedmixing and synthesis processes as well as better bulk properties of theobtained hydrophilic material.

The synthesis of a suitable hydrophilic silicone may be described asfollows:

This is the most preferred method as it is combined with a platinum saltcatalyzed cross-linking and give medical grade materials. The peroxideor tin salt catalyzed cross-linking can be used for non medical or nonbiocompatible applications or for parts that do not contact the skin.

A silicone precursor bearing reactive Si—H groups reacts with analpha-olefin sulfonate, wherein:

-   -   the values for n and m may range from about 1 to 26 or from 3 to        28, preferably range from 10 to 18, and more preferably from 10        to 12 or from 12 to 16,    -   the value for o ranges from about 1-10000, or from 5 to 1000,        and    -   wherein m, n, and o are independent of each other.

The olefin component may be strongly hydrophilic, because it may includea polar, negatively charged head group (—O3S) and a cation (Mn+) forcharge balance. The mixing of the hydrophilic olefin component with thehydrophobic silicone precursor may be hampered by the difference inhydrophilicity. It may be particularly different to suspend the ion paircomposed of the anionic head group and the cationic counterion in thehydrophobic matrix of the silicone precursor.

Adding a crown ether as a solubility or mixing mediator may be highlyeffective and may allow for a simple, rapid, and highly reproduciblesynthesis of the desired hydrophilic silicone material. The choice ofthe most suitable crown ether may depend on the counter cation used. Forinstance, the most efficient solubility mediator for dissolving sodiumions in hydrophobic media is the 15-crown-5 ether, whereas the mostsuitable solubility mediator for dissolving potassium ions inhydrophobic media is the 18-crown-6 crown ether. The stabilization ofmetal ions in hydrophobic media by crown ethers, derivatives thereof,and related molecules, is well known in the art and has been describedfor instance in the following publications, the content of which isincorporated herein by reference:

-   H. J. Schneider et al., Chemical Society Reviews, 2008, 37, 263-277;-   Barannikov, Russian Journal of Coordination Chemistry, 2002, 28,    153-162; and-   J. W. Steed, Coordination Chemistry Reviews, 2001, 215, 171-221; and    in references therein.

In an exemplary embodiment in accordance with the present invention,mixing a commercial silicone precursor material with a sodiumalpha-olefin sulfonate may be facilitated by the addition of a crownether mixing mediator. Sodium alpha-olefin sulfonates, such as sodiumC12-14 olefin sulfonate, sodium C14-16 olefin sulfonate, sodium C14-18olefin sulfonate, or sodium C16-18 olefin sulfonate, are mixtures oflong chain sulfonate salts prepared by the sulfonation of alpha olefins.The numbers indicate the average length of the carbon chains of thealpha olefins. Other ligating compounds that may be suitable to form aninclusion complex with the chosen counter ion may be used as analternative to crown ethers. An example of such compounds arecalix[4]arenes as described in B. S. Creaven et al., CoordinationChemistry Reviews, 2009, 253, pp. 893-962, the content of which isincorporated herein by reference.

The water-absorbing rubbery or elastomeric polymer material for use inthe user interface device, or wound dressing, with high water-uptakecapacity may be in the form of a fiber or fibrous material. Manufactureof polymer fibers, in particular silicone fibers such as used as fillersin polyester pillows, in particular hollow silicone fibers with a linearmass density from 1.5 to 25 deniers, are well known to the skilledperson.

The water-absorbing rubbery or elastomeric polymer material for use inthe user interface device, or wound dressing, with high water-uptakecapacity of the present invention may also be in the form of a polymerfoam, in particular a silicone-based foam, in which case a suitablesilicone-based foaming composition is required. This foaming compositionmay be defined for instance as comprising:

-   -   one or more hydrophobic organic monomers selected from the group        consisting of dialkylsiloxanes and diarylsiloxanes, or a        silicone precursor,    -   a monomer or polymer with one or more hydrophilic side groups,    -   one or more hydroxylated components,    -   from 1 to 250 ppm of a platinum catalyst, and optionally a foam        density-reducing amino component.

Exemplary details of such foaming compositions are provided below.

A hydroxyl source is necessary to properly blow the foamable compositionand may be in the form of one or more hydroxylated components. Thesource of hydroxyl may be selected from the group consisting of water,organic alcohols, silanols and mixtures thereof. Suitable silanolsinclude any hydroxylated organosiloxane having an average of 1 to 2.5silicon-bonded hydroxyl radicals per molecule. The silanols may bemonomers, homopolymers, copolymers or mixtures thereof. Examples ofsuitable silanols include, but are not limited to, hydroxyl end-cappedpolydimethylsiloxane, hydroxyl end-cappeddimethylsiloxane/phenylmethyl-siloxane copolymers, hydroxyl end-cappedpolymethyl-3,3,3-trifluoropropylsiloxane and diphenylmethylsilanol.

Organic alcohols suitable for use in the foaming compositions herein maybe mono-alcohols or polyols, preferably having from 1 to 12 carbonatoms. Suitable organic alcohols include, but are not limited to,ethanol, propanol, butanol, lauryl alcohol, octyl alcohol, ethyleneglycol, and benzyl alcohol. The hydroxyl source may react with hydrogenof the hydrophobic siloxane or silicone precursor to produce hydrogengas. Water will react with hydrogen of the hydrophobic siloxane orsilicone precursor to produce a hydroxyl function which can furtherreact to produce additional gas and a cross-link site. Thus, where wateris the hydroxyl source, additional gas will be generated as a benefit,but gassing after cure may occur. Silanol, due to good solubility in thecomposition, produces gas immediately but may lead to problems ofpremature gelation. Organic alcohols do not as easily react with thehydrogen function and thus are generally used in combination withsilanol or water. Depending on the hydroxyl source used, there shouldpreferably be from 0.02 to 5 hydroxyl groups from the hydroxyl sourcefor each silicone-bonded hydrogen atom in the hydrophobic siloxane orsilicone precursor. Alternatively the hydroxylated component(s) shouldconstitute not more than 2% by weight of the foamable composition of thepresent invention.

Suitable platinum catalysts are preferably soluble in the otheringredients of the foaming composition of the present invention.Although this is not a limiting feature of the present invention, theycan be selected from the group of compounds having the formulae(PtCl2.Olefin)2 and H(PtCl3.Olefin), as described in U.S. Pat. No.3,159,601. The olefin shown in these formulae is preferably an aliphaticalkene having from 2 to 8 carbon atoms, a cycloalkene having from 5 to 7carbon atoms, or an alkenylaryl compound such as styrene. Specificsuitable olefins include, but are not limited to, ethylene, propylene,butene, octene, cyclopentene, cyclohexene, and cycloheptene,

A further suitable platinum catalyst for the foaming composition of thepresent invention is the platinum chloride cyclopropane complex(PtCl2C3H6)2 described in U.S. Pat. No. 3,159,662, or a complex formedfrom chloroplatinic acid with up to 2 moles per gram of platinum of aligand selected from the group consisting of alcohols, ethers, aldehydesand mixtures thereof as described in U.S. Pat. No. 3,220,972.

Another suitable platinum catalyst (see U.S. Pat. No. 3,775,452) may beformed by reacting chloroplatinic acid containing 4 moles of water ofhydration with tetramethyltetravinylcyclosiloxane in the presence ofsodium bicarbonate in an ethanol solution.

Platinum catalysts such as illustrated above may be deposited oncarriers such as silica gel or powdered charcoal.

An amino compound optionally suitable and effective to lower siliconefoam density has the formula NR3 wherein each R is independentlyselected from the group consisting of hydrogen, hydroxyl, C1-18 alkyl,C3-10 cycloalkyl, aryl (e.g. phenyl), and silyl, provided that at mostone R may be hydroxy and provided that not all three R are hydrogen.Suitable amino compounds include, but are not limited to, hydroxylamines(e.g. diethyl hydroxyl amine), primary, secondary and tertiary amines,and silylamines, for example tetramethylpiperidine, piperidine,N-methylmorpholine, N,N-dimethyl-ethylenediamine, N-methylipiperidine,N-hexylamine, tributylamine, dibutylamine, cyclohexylamine,di-n-hexylamine, triethylamine, benzylamine, dipropylamine,N-ethyl-phenylamine, tetramethyl-guanidine, hexamethyl-disilazane andN-methylmorpholine. Preferably the amino compound should be soluble inthe foamable composition for use in the present invention.

Hydrophobic organic monomers suitable for the foaming compositions foruse in the invention include, but are not limited to, polysiloxaneshaving not less than 5 alkylhydrogensiloxane units per molecule,polysiloxanes having not less than two silicon-bonded hydroxyl groupsper molecule, fluorinated polyorganosiloxanes. Monomers or polymers withhydrophilic side groups suitable for the foaming compositions of theinvention are as described previously with respect to embodiments ofhydrophilic silicone materials.

Preferably, the foaming composition for use in the invention is providedin the form of two or more parts for admixture just prior to formingsaid composition, and each of said parts preferably has a similarviscosity as the other one at 25°.

Reactions of components of the foaming compositions to generate hydrogengas and to cure the mass through chain extension and crosslinking withinthe desired time span are dependent on presence of appropriateproportions of these components, especially the alkylhydrogenpolysiloxane. Preferably this polysiloxane should have from 0.5% to 2.5%by weight of silicon-bonded hydrogen atoms.

These components of the foaming compositions are preferably liquids withappropriate functionality and chain length to achieve the targetviscosity required for the composition, the amount of hydrogen evolutionand the degree of chain extension and crosslinking required duringcuring of the composition. Suitable polysiloxanes having silicon-bondedhydroxyl groups are preferably silanol terminated polydiorganosiloxanes.

One may optionally include, in the foaming hydrophilic siliconecomposition for use in the invention, appropriate amounts of higherfunctional materials as crosslinking agents. Suitable crosslinkingagents include materials having three or more functional, e.g. hydroxyl,groups per molecule. Preferred crosslinking agents include analkoxysilane and/or a condensation product thereof capable of combiningwith three or more hydroxy polysiloxane molecules with release of thecorresponding alcohol, e.g. methyl trimethoxysilane,n-propylortho-silicate or ethyl polysilicate.

The foaming compositions for use in the present invention may alsoinclude up to 10 percent, based on the weight of the hydrophobicsiloxane, of GSiO3/2 units wherein G is a residue obtained by removingthe hydrogen atom from a hydroxyl group of a linear organic polymerselected from the group consisting of homopolymers of ethylenicallyunsaturated alcohols, copolymers of these alcohols with ethylenicallyunsaturated hydrocarbons, polyethers and polyoxyalkylene glycols,wherein said organic polymer contains an average of at least oneterminal hydroxyl group per molecule, as described in European PatentNo. 179.598.

Within the above definitions of various embodiments of the foamingcompositions for use in the present invention, one may obtain rubbery orelastomeric silicone materials being in the form of a foam with a foamdensity from 60 to 300 kg/m3. For instance, high density foams from 150to 300 kg/m3, or low density foams from 60 to 150 kg/m3.

The following examples are purely illustrative of specific embodimentsand should not be understood or construes as limiting the scope of theinvention.

Example 1

The commercial silicone elastomer Elastosil LR 3004/40 (WackerSilicones, Germany) was used as silicone precursor material. Thesilicone precursor material is a two component system that has to bemixed in a 1:1 ratio of the two components A and B. The A componentconsists of a pre-polymer bearing reactive vinyl groups and a platinumcatalyst. The B component consists of a pre-polymer bearing reactivevinyl groups and a pre-polymer bearing Si—H groups. The siliconecomposition was comprised of 90% of the commercial silicone precursorand 10% of a commercial sodium alpha-olefin sulfonate.

The commercial sodium alpha-olefin sulfonate was first mixed with the Acomponent of the silicone precursor material. This mixing process isgenerally energy-demanding as the two components are viscous and do notmix well. An example of the energy/shear that is needed is given in theinternational patent application WO2010/095105, where the incorporationof the surfactant in Elastosil LR3003/60 is mentioned. Heating to 120°C. was needed to incorporate the surfactant. The used Elastosil 3004/40was found to be even more viscous than Elastosil LR3003/60.

To facilitate mixing of the commercial sodium alpha-olefin sulfonatewith the silicone precursor A component, a crown ether (15-crown-5) wasused (10% w/w with respect to the total amount of components A+B) as amixing mediator. After addition of the crown ether, mixing was found tobe straight forward and easily accomplished at room temperature.

More specifically, commercial sodium alpha-olefin sulfonate (2 g) wasmixed with 15-crown-5 (2 g) and silicone precursor A component (10 g).Mixing was performed at room temperature (SpeedMixer™ DAC 150 FVZ-K,Hauschild, Germany, 2×2 min, 3300 rpm). Then silicone precursor Bcomponent (11.4 g) was added and the obtained composition was mixedagain (SpeedMixer™ DAC 150 FVZ-K, Hauschild, Germany, 2×2 min, 3300rpm). The new silicone composition was thus comprised of 84% wt of thecommercial silicone precursor material, 8% wt of a commercial sodiumalpha-olefin sulfonate, and 8% wt of the mixing mediator 15-crown-S.

Material samples were prepared by casting the above mixture onto thesurface of a glass substrate and curing (30 min, 130° C.) under reducedpressure (<10 mbar). After curing, the water uptake of the new siliconematerial (sample A) was compared with that of two other materials: amaterial sample that was made with 20% wt of the sodium alpha-olefinsulfonate without crown ether (sample B) and a material sample that wasmade of the commercial silicone elastomer Elastosil 3004/40 according tothe instructions of the manufacturer (sample C). After immersion of allthree samples in demineralized water for 5 days, the Elastosil 3004/40(sample C) had taken up 0.3% wt of water, the new silicone materialcomprising the sodium alpha-olefin sulfonate and the crown ether mixingmediator (sample A) had taken up 43% wt of water, whereas the sample Bcomprising only the sodium alpha-olefin sulfonate but no 15-crown-5mixing mediator, had taken up 40% wt of water.

Water uptake (weight %) as a function of time of different amounts ofsodium C12-14 alkenyl sulfonate with equal amounts of 15-crown-5 inElastosil LR3004/40 along the route described herein are shown in FIG. 7.

As can be seen, a composition for the preparation of hydrophilicsilicone materials is disclosed in accordance to a one embodiment of thepresent invention, that enables improved mixing and synthesis processesleading to improved hydrophilic bulk properties of the obtainedhydrophilic silicone. The obtained hydrophilic silicone in accordancewith one embodiment of the present invention may be utilized in variouselements of a user or patient interface, such as cushions 41 andforehead pads 42 of patient interface 40, which may be, for example, amask for positive air pressure therapy of obstructive sleep apnea, inaccordance with another embodiment of the present invention. Thehydrophilic silicone including a silicone precursor material, a sodiumalpha-olefin sulfonate, and a crown ether mixing mediator may allow foran effective removal of moisture from the patient interface-skin contactarea by either uptake of the moisture in the hydrophilic silicone or bydiffusion of the moisture through the hydrophilic silicone away from auser interface, such as the face mask-skin contact region. Thus, animproved microclimate may be created at the patient interface-skincontact area, which may result in reduced moisture accumulation, reducedskin irritation, and reduced skin damage and reduced red mark formation.

In the following examples 2-5, the amount of commercial sodium C12-14alkenyl sulfonate added to the amount of silicone precursors A+B isgiven in percentage and calculated along weight sodium C12-14 alkenylsulfonate/weight silicone A+B*100. The values for the precentagesilicone precursor A+B given in the examples 2-5 are the values for100%−amount sodium C12-14 alkenyl sulfonate %.

Example 2

The commercial silicone elastomer Elastosil LR 3004/40 (WackerSilicones, Germany) was used as silicone precursor material. Thesilicone precursor material is a two component system that was mixed ina 1:1 weight ratio of two components A and B. The A component consistsof a silicone pre-polymer bearing reactive vinyl groups and a platinumcatalyst. The B component consists of a silicone pre-polymer bearingreactive vinyl groups and a pre-polymer bearing Si—H groups.

The sodium alpha-olefin sulfonate RCH═CH(CH2)nSO3Na (n=12-14)commercially available from The Chemistry Store.com (Cayce, S.C., UnitedStates) with an average particle size above 400 μm was first mixed withthe A component of the silicone precursor material. This mixing processis generally energy-demanding as the two components are viscous and donot mix well. Heating to 120° C. may therefore be needed.

To facilitate mixing of the commercial sodium alpha-olefin sulfonatewith the silicone precursor A component, a crown ether (15-crown-5)acetone mixture was used as a mixing mediator. After addition of thecrown ether and acetone mixing was found to be straight forward andeasily accomplished at room temperature.

More specifically, the commercial sodium alpha-olefin sulfonate (12 g)was mixed in a first step with 15-crown-5 (7 g) and 7 g acetone. Afterthis the silicone precursor A component (19 g) was added. Mixing wasperformed at room temperature (Speed Mixer™ DAC 150 FVZ-K, Hauschild,Germany, twice 2 minutes, 3300 rpm). The crown ether and acetone wereremoved in vacuum at 0.05 mbar, 90° C. Then silicone precursor Bcomponent (26.1 g) was added and the obtained composition was mixedagain (same mixer, twice 2 minutes, 3300 rpm). The resulting siliconecomposition was thus comprised of 73.4% by weight of the commercialsilicone precursor material, and 26.6% by weight of the commercialsodium alpha-olefin sulfonate.

Material samples were prepared by casting the above mixture onto thesurface of a glass substrate and curing (30 minutes, 130° C.) under N2atmosphere.

Example 3

In a further example the commercial silicone elastomer Elastosil LR3004/40 (Wacker Silicones, Germany) was used as silicone precursormaterial. The silicone precursor material is a two component system thatwas mixed in a 1:1 weight ratio of two components A and B. The Acomponent consists of a silicone pre-polymer bearing reactive vinylgroups and a platinum catalyst. The B component consists of a siliconepre-polymer bearing reactive vinyl groups and a pre-polymer bearing Si—Hgroups.

A commercial sodium alpha-olefin sulfonate RCH═CH(CH2)nSO3Na (n=12-14)from Stepan Company was used. This very fine powder with particle sizes<400 um was mixed with the A component of the silicone precursormaterial by speed mixing. More specifically, commercial sodiumalpha-olefin sulfonate (12 g) was mixed with silicone precursor Acomponent (19 g). Then silicone precursor B component (26.1 g) was addedand the obtained composition was mixed. The resulting siliconecomposition was thus comprised of 73.4% by weight of the commercialsilicone precursor material, and 26.6% by weight of a commercial sodiumalpha-olefin sulfonate.

Patient interface devices were prepared by pressure molding at 130° C.(see FIG. 4 b for an example of the device).

Example 4

In a further example the commercial silicone elastomer Elastosil LR3004/40 (Wacker Silicones, Germany) was used as silicone precursormaterial. The silicone precursor material is a two component system thatwas mixed in a 1:1 weight ratio of two components A and B. The Acomponent consists of a silicone pre-polymer bearing reactive vinylgroups and a platinum catalyst. The B component consists of a siliconepre-polymer bearing reactive vinyl groups and a pre-polymer bearing Si—Hgroups.

A commercial sodium alpha-olefin sulfonate RCH═CH(CH2)nSO3Na (n=12-14)from Stepan Company was used. This very fine powder (12 g) was mixedwith 7 g ethanol. Then 19 g of the A component of the silicone precursormaterial added and mixing was carried out with a speed mixer. Aftermixing the ethanol was removed under vacuum at 60 oc. Then siliconeprecursor B component (26.1 g) was added and the obtained compositionwas mixed. The resulting silicone composition was thus comprised of73.4% by weight of the commercial silicone precursor material, and 26.6%by weight of a commercial sodium alpha-olefin sulfonate.

Patient interface devices were prepared by pressure molding at 130° C.(see FIG. 4 b for an example of the device).

Example 5

In a further example the commercial silicone elastomer Elastosil LR3004/40 (Wacker Silicones, Germany) was used as silicone precursormaterial. The silicone precursor material is a two component system thatwas mixed in a 1:1 weight ratio of two components A and B. The Acomponent consists of a silicone pre-polymer bearing reactive vinylgroups and a platinum catalyst. The B component consists of a siliconepre-polymer bearing reactive vinyl groups and a pre-polymer bearing Si—Hgroups.

A commercial sodium alpha-olefin sulfonate RCH═CH(CH2)nSO3Na (n=12-14)from Stepan Company was used. This very fine powder 12 g was mixed with7 g of an ethanol water mixture (50/50% by volume). Then 19 g of the Acomponent of the silicone precursor material added and mixing wascarried out with a speed mixer. After mixing the ethanol was removedunder vacuum at 90° C. Then silicone precursor B component (26.1 g) wasadded and the obtained composition was mixed. The resulting siliconecomposition was thus comprised of 73.4% by weight of the commercialsilicone precursor material, and 26.6% by weight of a commercial sodiumalpha-olefin sulfonate.

Patient interface devices were prepared by pressure molding at 130° C.(see FIG. 4 b of the device).

Water uptake (weight %) as a function of time of different mixingmethods of sodium C12-14 alkenyl sulfonate with Elastosil LR3004/40along the above route described in examples 2-5 is given in FIG. 8 .

Example 6

In a further example in a 2.5 litre jacketed glass reactor a mixture of55 grams butylmethacrylate (BMA) (99%+) and 2200 grams water of aconductivity of 18.2 MΩ·cm and a 0.6 g commercial sodium alpha-olefinsulfonate RCH═CH(CH2)nSO3Na (n=12-14) from Stepan Company are mixed anddegassed under nitrogen while stirring at 500 rpm (using a double bladedstirrer). In order to reduce the chain length of the polymer, bycontrolling the micelle size of the BMA droplets in water, from 1 to 2%by weight of surfactant (e.g. sodium alpha-olefin sulfonate) is added tothe monomer mixture. Then the reactor is put under nitrogen and themixture is heated to 80° C. After addition of the initiator solution(for instance 1.6 g ammonium persulfate 98% in 50 g of water of aconductivity of 18.2 MΩ·cm) at 80° C., the stirring speed is reduced to350 rpm. Polymerisation is carried out for at least 3 hours.

Example 7

In this example the commercial silicone elastomer Elastosil LR 3003/5(commercially available from Wacker Silicones, Germany) was used as thesilicone precursor material. The silicone precursor material is a twocomponent system that was normally mixed in a 1:1 weight ratio of twocomponents A and B. The A component consists of a silicone pre-polymerbearing reactive vinyl groups and a platinum catalyst. The B componentconsists of a silicone pre-polymer bearing reactive vinyl groups and apre-polymer bearing Si—H groups. A commercial sodium alpha-olefinsulfonate RCH═CH(CH2)nSO3Na (n=12-14) from Stepan Company (Northfield,Ill., United States) was used. 12 g of this very fine powder (particlesizes below 400 μm) was mixed with 7 g of an ethanol water mixture(50/50% by volume). Then 19 g of the A component of the siliconeprecursor material was added and mixed with a speed mixer. After mixingthe ethanol and water were removed under vacuum at 60° C. until a smallamount (±0.5 gram) of water was still present. Then silicone precursor Bcomponent (24.7 g) was added and the obtained composition was mixed. Thecommercial sodium alpha-olefin sulfonate added to the siliconeprecursors A+B, is thus amounting to 27.5 weight % of silicone precursor(A+B) weight ((weight sodium alpha-olefin sulfonate/weight siliconeA+B)*100). The mixing ratio of this system for component A to B was 1 to1.3. Material samples were prepared by pressure molding at 130° C. for10 to 15 minutes at 711 psi.

While the invention has been described by reference to various specificembodiments, it should be understood that numerous changes may be madewithin the spirit and scope of the inventive concepts described.Accordingly, it is intended that the invention not be limited to thedescribed embodiments, but will have full scope defined by the languageof the following claims.

The invention claimed is:
 1. A process for preparing a rubbery orelastomeric polymer material, comprising the steps of: providing ahydrophobic organic monomer or pre-polymer; providing a hydrophilicmonomer being an alkenyl sulfonate having 3 to 28 carbon atoms inassociation with a cation; providing a ligating compound for thehydrophilic monomer; and polymerizing the hydrophobic organic monomer orpre-polymer in the presence of the hydrophilic monomer until obtaining arubbery or elastomeric polymer material, wherein repeating units fromthe one or more hydrophobic organic monomer or pre-polymer are modifiedwith hydrophilic groups from the one or more hydrophilic monomer,further comprising the steps of: combining the hydrophobic organicmonomer or pre-polymer, the hydrophilic monomer, and the ligatingcompound, wherein the amount of the ligating compound is sufficient todissolve the cation and achieve solubility or miscibility of thehydrophilic monomer in the hydrophobic organic monomer or pre-polymer;and producing the rubbery or elastomeric polymer material, wherein therubbery or elastomeric polymer material takes up more than 5% by weightand up to 500% by weight, of water after immersion in demineralizedwater at room temperature for a sufficient time to reach saturation. 2.A process according to claim 1, wherein the rubbery material comprisesat least one material represented by the following structural formula:

R═Si(CH₃)₃ or H wherein each R is Si(CH₃)₃ or hydrogen, n is from 3 to28, the total number (m+o+1) of repeating units is at least 5 and lessthan 1,000, and n and o are integers independently selected from eachother and being at least 6.